EP3841060A1 - Methods for the degradation of sf6 - Google Patents
Methods for the degradation of sf6Info
- Publication number
- EP3841060A1 EP3841060A1 EP18793624.0A EP18793624A EP3841060A1 EP 3841060 A1 EP3841060 A1 EP 3841060A1 EP 18793624 A EP18793624 A EP 18793624A EP 3841060 A1 EP3841060 A1 EP 3841060A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- groups
- ylene
- ylidenmethyl
- ylidenamino
- phosphine
- 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.)
- Withdrawn
Links
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 20
- 230000015556 catabolic process Effects 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 27
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 22
- 239000003446 ligand Substances 0.000 claims abstract description 5
- -1 carbanions Chemical group 0.000 claims description 88
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- 125000005549 heteroarylene group Chemical group 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 125000000732 arylene group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000006588 heterocycloalkylene group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000005265 dialkylamine group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000000369 oxido group Chemical group [*]=O 0.000 claims description 2
- 229910018503 SF6 Inorganic materials 0.000 description 29
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000003386 piperidinyl group Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229960000909 sulfur hexafluoride Drugs 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- SRGQEZQRKDZRHA-UHFFFAOYSA-N F[PH3]F Chemical compound F[PH3]F SRGQEZQRKDZRHA-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000000160 oxazolidinyl group Chemical group 0.000 description 3
- 230000037361 pathway Effects 0.000 description 3
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 125000004193 piperazinyl group Chemical group 0.000 description 3
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical compound S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 description 3
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 3
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PFRDRCIPKPEULG-UHFFFAOYSA-N imidazol-2-imine Chemical class N=C1N=CC=N1 PFRDRCIPKPEULG-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 125000002757 morpholinyl group Chemical group 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 239000011574 phosphorus Chemical class 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 125000001425 triazolyl group Chemical group 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 1
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 1
- KDCBVVQAMMXRFB-UHFFFAOYSA-N 1,4,7,10,13-pentazacyclopentadecane Chemical compound C1CNCCNCCNCCNCCN1 KDCBVVQAMMXRFB-UHFFFAOYSA-N 0.000 description 1
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical compound C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 description 1
- OZFOKTZBDJXZTE-UHFFFAOYSA-N 1,4,7-oxadiazonane Chemical compound C1CNCCOCCN1 OZFOKTZBDJXZTE-UHFFFAOYSA-N 0.000 description 1
- CIBAIKDMTBNPNQ-UHFFFAOYSA-N 1,4,7-thiadiazonane Chemical compound C1CNCCSCCN1 CIBAIKDMTBNPNQ-UHFFFAOYSA-N 0.000 description 1
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- PQNPKQVPJAHPSB-UHFFFAOYSA-N 1,4,7-trithionane Chemical compound C1CSCCSCCS1 PQNPKQVPJAHPSB-UHFFFAOYSA-N 0.000 description 1
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 description 1
- 125000005940 1,4-dioxanyl group Chemical group 0.000 description 1
- DXVOEFOMGMELCV-UHFFFAOYSA-N 1-butylpyridin-4-imine Chemical compound CCCCN1C=CC(=N)C=C1 DXVOEFOMGMELCV-UHFFFAOYSA-N 0.000 description 1
- VOMIZDGXPZOXKH-UHFFFAOYSA-N 3h-pyridin-4-imine Chemical group N=C1CC=NC=C1 VOMIZDGXPZOXKH-UHFFFAOYSA-N 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- MOYDRKKZEHROID-UHFFFAOYSA-N benzimidazol-2-imine Chemical group C1=CC=CC2=NC(=N)N=C21 MOYDRKKZEHROID-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
- 238000002600 positron emission tomography Methods 0.000 description 1
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/45—Compounds containing sulfur and halogen, with or without oxygen
- C01B17/4507—Compounds containing sulfur and halogen, with or without oxygen containing sulfur and halogen only
- C01B17/4515—Compounds containing sulfur and halogen, with or without oxygen containing sulfur and halogen only containing sulfur and fluorine only
- C01B17/453—Sulfur hexafluoride
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6503—Five-membered rings
- C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
Definitions
- alkyl linear and branched Cl-C8-alkyl
- long-chain alkyl linear and branched C5-C20 alkyl
- alkenyl C2-C6-alkenyl
- cycloalkyl C3-C8-cycloalkyl
- alkoxy Cl-C6-alkoxy
- long-chain alkoxy linear and branched C5-C20 alkoxy alkylene: selected from the group consisting of:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
Abstract
The following invention relates to the degradation of SF6 with a trivalent phosphine having at least one ligand which has π-donating characteristics. This leads to a smooth and quantitave degradation of the SF6.
Description
Methods for the degradation of SF6
D e s c r i p t i o n
The following invention relates to the activation and degradation of Sulfurhexaflouride, SF6.
Although sulfur hexafluoride SF6 has been recognized as the most potent greenhouse gas in the atmosphere, it is widely used in a variety of industrial applications and processes owing to its unique physical and chemical properties such as a high dielectric constant, low toxicity and its extreme chemical inertness. The 100 year global warming potential of SF6 is 23500 times higher than that of C02 as a result of its high radiative efficiency and long atmospheric lifetime of about 3200 years. Therefore, safe and efficient methods for its depletion are required. Typical technical methods include electrical or plasma discharge technologies, which not only suffer from the high energy consumption, but also yield especially toxic and corrosive decomposition products, cf. Zamostna and Braun, Nachrichten aus der Chemie 2016, 829-835. Therefore there is a constant need for methods for the degradation and/or activation of SF6 and it is an object to provide alternative methods which idealiter can be performed under mild conditions and possibly lead to products which have commercial and/or chemical interest.
This object is solved by the method of Claim 1. Accordingly a method for the activation and/or degradation of SF6 is provided comprising the step of contacting SF6 with a phosphine PRXR2R3, whereby at least one of the R1 to R3 is a moiety which has π-donating
characteristics.
The term "π-donating characteristics" in the sense of the present invention especially means that the atom in a-position to the phosphorus atom of the phosphine has at least one lone pair of electrons that can donate electron density towards the phosphorus atom thus increasing the phoshine's basicity. The moiety which has π-donating characteristics can according to a preferred embodiment be neutral or the moiety which has π-donating characteristics can according to a preferred embodiment be anionic.
Surprisingly it has been found that these compounds are able to react with SF6. For most applications within the present invention at least one or more of the following advantages can be observed:
- The reaction occurs at low temperatures, starting from -78°C or at room temperature
The reaction is very fast
The reaction does not require any additional activation
The reaction is quantitative with respect to the SF6
The reaction products are of chemical interest
- The reaction products can be used as fluorinating agents in chemical synthesis
The reaction products are temperature- stable solids
The reaction products are non-toxic
The inventors have found that the degradation of the SF6 in most applications follows one of the following two reaction pathways: a) Formation of two reaction products, i.e. P(=S)R1R2R3 and PR1R2R3F2.
b) Formation of the salt PR^R^"1" SF5 " which is in most applications isolatable.
It has been found that pathway a) more likely occurs when not all of the R1 to R3 have a π- donating characteristics, whereas when all of the R1 to R3 have a π-donating characteristics in many cases pathway b) is followed. As stated above, the reaction products are of chemical and/or commercial interest since they can be used as fluorine donor in suitable applications. Moreover, since 18F- substituted sulfurhexafluoride is commercially available, the inventive degradation process offers the possibility to synthesize 18F-labeled chemical compounds which are of high interest, e.g. in pharmaceutical and medical applications such as positron-emission tomography (PET) imaging.
According to a preferred embodiment of the present invention, the phosphine does not form a part of a metal complex and/or is not a ligand to a metal during the activation and/or degradation of SF6.
According to a preferred embodiment of the present invention, the phosphine does not form a part of a Rhodium complex and/or is not a ligand to Rhodium during the activation and/or degradation of SF6. So it is a further object of the present invention to provide new fluorinating and/or fluor- donating products obtainable from SF6.
Accordingly PR1R2R3F+ SF5 " and PR1R2R3F2 are provided with R1 to R3 as defined in this invention.
The present invention also relates to the use of PR1R2R3F+ SF5 " and/or PR1R2R3F2 in fluorination reactions
According to a preferred embodiment the moiety which has π-donating characteristics comprises a structure -A-B with
A = :N-¾- .C-¾-
• · R
with R4, R5, R8, R16 being selected independently from each other hydrogen, alkyl, long- chain alkyl, alkenyl, cycloalkyl, alkoxy, long chain alkoxy, alkylene, aryl, arylene, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, and with R6, R7, R9 to R15 being selected independently from each other hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, alkoxy, long chain alkoxy, alkylene, aryl, arylene, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, dialkylamine, whereby two suitable substituents may form a ring, especially an aromatic ring.
According to a preferred alternative embodiment the moiety which has π-donating
characteristics comprises a structure -A-B with
with M+ being selected from alkali and Mg-Halogenide,
R17 and R18 being selected independently from each other hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, alkoxy, long chain alkoxy, alkylene, aryl, arylene, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, dialkylamine whereby two suitable substituents may form a ring, especially an aromatic ring.
Generic group definition: Throughout the description and claims generic groups have been used, for example alkyl, alkoxy, aryl. Unless otherwise specified the following are preferred groups that may be applied to generic groups found within compounds disclosed herein: alkyl: linear and branched Cl-C8-alkyl, long-chain alkyl: linear and branched C5-C20 alkyl alkenyl: C2-C6-alkenyl, cycloalkyl: C3-C8-cycloalkyl, alkoxy: Cl-C6-alkoxy, long-chain alkoxy: linear and branched C5-C20 alkoxy alkylene: selected from the group consisting of:
methylene; 1,1-ethylene; 1,2-ethylene; 1,1 -prop ylidene; 1,2-propylene; 1,3- propylene; 2,2- propylidene; butan-2-ol-l,4-diyl; propan-2-ol-l,3-diyl; 1, 4-butylene; cyclohexane- 1,1 -diyl; cyclohexan-l,2-diyl; cyclohexan-1,3- diyl; cyclohexan-l,4-diyl; cyclopentane- 1,1 -diyl; cyclopentan-l,2-diyl; and cyclopentan-l,3-diyl, aryl: selected from homoaromatic compounds having a molecular weight under 300,
arylene: selected from the group consisting of: 1,2-phenylene; 1,3- phenylene; 1,4-phenylene;
1.2- naphtalenylene; 1,3-naphtalenylene; 1,4- naphtalenylene; 2,3-naphtalenylene; 1-hydroxy-
2.3- phenylene; l-hydroxy-2,4- phenylene; l-hydroxy-2,5- phenylene; and l-hydroxy-2,6- phenylene, heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, heteroarylene: selected from the group consisting of: pyridindiyl; quinolindiyl; pyrazodiyl; pyrazoldiyl; triazolediyl; pyrazindiyl; and imidazolediyl, wherein the heteroarylene acts as a bridge in the compound via any atom in the ring of the selected heteroarylene, more specifically preferred are: pyridin-2, 3-diyl; pyridin-2,4-diyl; pyridin-2,5-diyl; pyridin-2,6- diyl; pyridin-3,4- diyl; pyridin-3,5-diyl; quinolin-2,3-diyl; quinolin-2,4-diyl; quinolin-2, 8- diyl; isoquinolin-1, 3-diyl; isoquinolin-l,4-diyl; pyrazol-1, 3-diyl; pyrazol-3,5- diyl; triazole- 3,5-diyl; triazole-1, 3-diyl; pyrazin-2,5-diyl; and imidazole-2,4-diyl, a -C1-C6- heterocycloalkyl, wherein the heterocycloalkyl of the -CI -C6-heterocycloalkyl is, selected from the group consisting of: piperidinyl; piperidine; 1,4-piperazine, tetrahydrothiophene; tetrahydrofuran; 1,4,7-triazacyclononane; 1,4,8,11- tetraazacyclotetradecane; 1,4,7,10,13- pentaazacyclopentadecane; 1,4-diaza- 7-thia-cyclononane; 1,4- diaza-7-oxa-cyclononane; 1,4,7, 10-tetraazacyclododecane; 1,4-dioxane; 1,4, 7-trithia-cyclononane; pyrrolidine; and tetrahydropyran, wherein the heterocycloalkyl may be connected to the -Cl-C6-alkyl via any atom in the ring of the selected heterocycloalkyl, heterocycloalkylene: selected from the group consisting of: piperidin-1,2- ylene; piperidin- 2,6-ylene; piperidin-4,4-ylidene; l,4-piperazin-l,4-ylene; l,4-piperazin-2,3-ylene; 1,4- piperazin-2,5-ylene; l,4-piperazin-2,6-ylene; 1,4-piperazin- 1,2-ylene; l,4-piperazin-l,3-
ylene; l,4-piperazin-l,4-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene; tetrahydrothiophen-2,3-ylene; tetrahydrofuran-2,5-ylene; tetrahydrofuran- 3,4-ylene;
tetrahydrofuran-2,3-ylene; pyrrolidin-2,5-ylene; pyrrolidin-3,4-ylene; pyrrolidin-2,3-ylene; pyrrolidin- 1,2- ylene; pyrrolidin-l,3-ylene; pyrrolidin-2,2-ylidene; l,4,7-triazacyclonon-l,4- ylene; 1,4,7- triazacyclonon-2,3-ylene; l,4,7-triazacyclonon-2,9-ylene; 1,4,7-triazacyclonon- 3,8-ylene; l,4,7-triazacyclonon-2,2- ylidene; 1,4,8,1 l-tetraazacyclotetradec-l,4-ylene;
1,4,8,11- tetraazacyclotetradec-l,8-ylene; 1,4,8,1 l-tetraazacyclotetradec-2,3-ylene; 1,4,8,11- tetraazacyclotetradec-2,5-ylene; 1,4,8,11- tetraazacyclotetradec-l,2-ylene; 1,4,8,11- tetraazacyclotetradec-2,2-ylidene; 1 ,4,7, 10-tetraazacyclododec- 1 ,4-ylene; 1 ,4,7, 10- tetraazacyclododec-l,7-ylene; 1,4,7,10-tetraazacyclododec- 1,2- ylene; 1,4,7,10- tetraazacyclododec-2,3- ylene; 1,4,7, 10-tetraazacyclododec-2,2-ylidene; 1,4,7,10,13 pentaazacyclopentadec-l,4-ylene; 1,4,7,10,13- pentaazacyclopentadec-l,7-ylene; 1,4,7,10,13- pentaazacyclopentadec-2,3- ylene; 1,4,7, 10, 13-pentaazacyclopentadec-l,2-ylene; 1,4,7,10, 13-pentaazacyclopentadec-2,2-ylidene; l,4-diaza-7-thia-cyclonon- 1,4-ylene; l,4-diaza-7- thia-cyclonon-l,2-ylene; l,4-diaza-7thia-cyclonon- 2,3-ylene; l,4-diaza-7-thia-cyclonon-6,8- ylene; l,4-diaza-7-thia-cyclonon- 2,2-ylidene; l,4-diaza-7-oxacyclonon- 1,4-ylene; 1,4-diaza-
7- oxa-cyclonon- 1,2-ylene; l,4diaza-7-oxa-cyclonon-2,3-ylene; l,4-diaza-7-oxa-cyclonon-6,
8- ylene; l,4-diaza-7-oxa-cyclonon-2,2-ylidene; l,4-dioxan-2,3-ylene; 1,4- dioxan-2,6-ylene; 1 ,4-dioxan-2,2-ylidene; tetrahydropyran-2,3-ylene; tetrahydropyran-2,6-ylene;
tetrahydropyran-2,5-ylene; tetrahydropyran-2,2- ylidene; l,4,7-trithia-cyclonon-2,3-ylene; l,4,7-trithia-cyclonon-2,9- ylene; and l,4,7-trithia-cyclonon-2,2-ylidene, heterocycloalkyl: selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1,4-piperazinyl; tetrahydrothiophenyl;
tetrahydrofuranyl; 1,4,7- triazacyclononanyl; 1,4,8, 11 -tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl; l,4-diaza-7-thiacyclononanyl; l,4-diaza-7-oxa- cyclononanyl; 1,4,7, 10-tetraazacyclododecanyl; 1,4-dioxanyl; 1,4,7- trithiacyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl.
Unless otherwise specified the following are more preferred group restrictions that may be applied to groups found within compounds disclosed herein: alkyl: linear and branched Cl-C6-alkyl, more preferred methyl, ethyl, propyl, isopropyl, buyl, isobutyl long-chain alkyl: linear and branched C5-C10 alkyl, preferably linear C6-C8 alkyl alkenyl: C3-C6-alkenyl, cycloalkyl: C6-C8-cycloalkyl, alkoxy: Cl-C4-alkoxy, long-chain alkoxy: linear and branched C5-C10 alkoxy, preferably linear C6-C8 alkoxy alkylene: selected from the group consisting of: methylene; 1,2-ethylene; 1,3-propylene; butan-2-ol-l,4-diyl; 1,4-butylene; cyclohexane-l,l-diyl; cyclohexan-l,2-diyl; cyclohexan-1,4- diyl; cyclopentane-l,l-diyl; and cyclopentan-l,2-diyl, aryl: selected from group consisting of: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl, arylene: selected from the group consisting of: 1,2-phenylene; 1,3- phenylene; 1,4-phenylene; 1,2-naphtalenylene; 1,4-naphtalenylene; 2,3- naphtalenylene and l-hydroxy-2,6-phenylene, heteroaryl: selected from the group consisting of:
pyridinyl; pyrimidinyl; quinolinyl; pyrazolyl; triazolyl; isoquinolinyl; imidazolyl; and oxazolidinyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, heteroarylene: selected from the group consisting of: pyridin
2.3- diyl; pyridin-2,4-diyl; pyridin-2,6-diyl; pyridin-3,5-diyl; quinolin-2,3-diyl; quinolin-2,4- diyl; isoquinolin-l,3-diyl; isoquinolin-l,4-diyl; pyrazol-3,5-diyl; and imidazole-2,4-diyl, heterocycloalkyl: selected from the group consisting of:
pyrrolidinyl; morpholinyl; piperidinyl; piperidinyl; 1,4 piperazinyl; tetrahydrofuranyl; 1,4,7- triazacyclononanyl; 1,4,8,11-tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl; 1,4,7, 10-tetraazacyclododecanyl; and piperazinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl, heterocycloalkylene: selected from the group consisting of:
piperidin-2,6-ylene; piperidin-4,4-ylidene; l,4-piperazin-l,4-ylene; l,4-piperazin-2,3-ylene;
1.4- piperazin-2,6-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene;
tetrahydrofuran-2,5-ylene; tetrahydrofuran-3,4-ylene; pyrrolidin-2,5-ylene; pyrrolidin-2,2- ylidene; l,4,7-triazacyclonon-l,4- ylene; l,4,7-triazacyclonon-2,3-ylene; 1,4,7- triazacyclonon-2,2-ylidene; 1,4,8,11- tetraazacyclotetradec-l,4-ylene; 1,4,8,11- tetraazacyclotetradec-l,8-ylene; 1,4,8,1 l-tetraazacyclotetradec-2,3-ylene; 1,4,8,11- tetraazacyclotetradec-2,2-ylidene; 1 ,4,7, 10-tetraazacyclododec- 1 ,4-ylene; 1 ,4,7, 10- tetraazacyclododec- 1 ,7-ylene; 1 ,4,7,10-tetraazacyclododec-2,3-ylene; 1 ,4,7 , 10- tetraazacyclododec-2,2-ylidene; 1,4,7,10,13- pentaazacyclopentadec-l,4-ylene; 1,4,7,10,13- pentaazacyclopentadec-l,7-ylene; l,4-diaza-7-thia-cyclonon-l,4 ylene; l,4-diaza-7-thia- cyclonon-2,3-ylene; l,4-diaza-7-thia cyclonon-2,2-ylidene; l,4-diaza-7-oxa-cyclonon-l,4- ylene; 1,4 diaza-7-oxa-cyclonon-2,3-ylene;l,4-diaza-7-oxa-cyclonon-2,2- ylidene; 1,4- dioxan-2,6-ylene; l,4-dioxan-2,2-ylidene; tetrahydropyran-2,6-ylene; tetrahydropyran-2,5- ylene; and tetrahydropyran- 2,2-ylidene, a -Cl-C6-alkyl-heterocycloalky, wherein the heterocycloalkyl of the -CI- C6-heterocycloalkyl is selected from the group consisting of: piperidinyl; 1,4-piperazinyl; tetrahydrofuranyl; 1,4,7- triazacyclononanyl; 1,4,8,11- tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl; 1,4,7,10-
tetraazacyclododecanyl; and pyrrolidinyl, wherein the heterocycloalkyl may be connected to the -C1-C6- alkyl via any atom in the ring of the selected heterocycloalkyl,
According to a preferred embodiment of the present invention, the moiety which has π- donating characteristics is selected out of amido groups, carbanions, oxido group or out of the neutral groups comprising imidazol-2-ylidenamino groups, imidazolin-2-ylidenamino groups, imidazolidin-2-ylidenamino groups, benzimidazolin-2-ylidenamino groups, imidazolin-4- ylidenamino groups, imidazol-2-ylidenmethyl groups, imidazolin-2-ylidenmethyl groups, imidazolidin-2-ylidenmethyl groups, benzimidazolin-2-ylidenmethyl groups, imidazolin-4- ylidenmethyl groups, pyridine-2-ylidenamino groups, pyridine-4-ylidenamino groups, pyridine-2-ylidenmethyl groups, pyridine-4-ylidenmethyl groups, phosphoranylidenamino groups, phosphoranylidenmethyl groups and mixtures thereof.
According to a preferred embodiment of the present invention, the moiety which has π- donating characteristics comprises imines.
In the sense of the present invention, the term "imine" especially means and/or includes the structure -N=X with X being further substituted carbon and/or phosphorus. It should be noted that not all of the possible compounds which fall under that definition are usually called imines, however, in the sense of the present invention, they may especially be regarded as imines, too.
Especially preferred are imines in which the carbon is part of a six-membered heterocyclic ring comprising at least one nitrogen. In this regard it is especially advantageous if the carbon is in 2- or 4-position to a nitrogen.
According to a preferred embodiment of the present invention, the moiety which has π- donating characteristics comprises imidazolimines.
In the sense of the present invention the term "imidazolimines" especially means and/or includes the structure
whereby R4 and R5 are selected from the group comprising hydrogen, aryl and alkyl and whereby R7 and R8 may form a ring, especially an aromatic ring. The bond between the carbon atoms at R6 and R7 may be a single or a (at least formal) double bond.
According to a preferred embodiment, all three of the R1 to R3 have has π-donating characteristics. In this case it is especially preferred that R1 to R3 are identical.
However, the present invention is not limited to that and according to a preferred embodiment of the present invention at least one of the R1 to R3 does not have π-donating characteristics. In this case especially alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups or dialkylamino groups are preferred as substituents bound to phosphorus.
It should be noted that according to a preferred embodiment of the present invention, the phosphine is not isolated before it is contacted with the SF6. It has been shown that for many applications within the present invention this is not necessary for degradation of the SF6.
According to a preferred embodiment, the inventive method is carried out at a temperature between > -78°C and < 60°C, preferably > 20°C and < 30°C, more preferred at room temperature.
According to a preferred embodiment, the inventive method is carried out in a solvent. The solvent is preferably a non-protic organic solvent, more preferred THF, DMF, acetonitrile, benzene, toluene, m-xylene, hexane, pentane, heptane, cyclohexane, 1,4-dioxane, diethyl ether, Ethyl acetate or mixtures thereof.
Alternatively the inventive method is carried out with the phosphine applied on a solid carrier. This especially allows the reaction to occur in a flow-through fashion without the need for a solvent. Possible solid carrier materials include silica zeolites, diatomaceous earth, silicon dioxide (silica), aluminium oxide (alumina), carbon and mixtures thereof.
In case the inventive method is carried out with the phosphine applied on a solid carrier it is especially preferred that before the gas which is to be cleaned from SF6 before reaching the phosphine is removed from water and/or oxygen and/or C02 since these compounds also often react with the phosphine. This can be achieved by known methods in the art, e.g. by passing the gas through molecular sieves or a charcoal filter.
The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.
Additional details, characteristics and advantages of the object of the invention are disclosed in the subclaims and the following description of the respective examples and embodiments— which in an exemplary fashion— show preferred embodiments according to the invention. Such examples do not necessarily represent the full scope of the invention, however, and reference is made therefore to the claims and herein for interpreting the scope of the invention. It is to be understood that both the foregoing general description and the following
detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed.
EXAMPLE I:
Isolation of:
(Compound 1)
A solution of P(NI Pr)3 (465 mg, 757,4 mmol) in diethyl ether (10 mL) was pressurized with 2 bar sulfur hexafluoride pressure for 45 minutes. The crystalline component was filtered off and the crystals were washed with diethyl ether (3 x 3 mL). The filtrate was evaporated to dryness. Compound 1 was isolated as a crystalline solid in 92% yield. 1 showed good solubility and stability in acetonitrile, THF, dichloromethane, chloroform and
difluorobenzene. 1 is insoluble in benzene, toluene, hexane or diethyl ether. An NMR analysis revealed that solid 1 is stable at temperatures up to 145 °C and slowly decomposed at temperatures higher than 150 °C. No decomposition took place upon storage of 1 under argon atmosphere for 4 months. After exposure of solid 1 to air for one hour decomposition was detected in the NMR spectra.
EXAMPLE II:
In the following SF6 was allowed to react with a phosphine having two imidazolimine and one isopropyl substituents according to the following reaction:
The NMR study to verify the degradation of sulfur hexafluoride with the phosphine was performed in C6D6 under 1 bar SF6 pressure. After 36 h at room temperature complete conversion of phosphine could be observed. The two resonances in the 31P NMR spectrum for the phosphine sulfide (45.4 ppm, 16 Hz) and the difluorophosphoran (-59.2 ppm; t,
^PF = 606.0 Hz) verify the clean degradation of SF6 into two species. The resonance for the difluorophosphoran (-32.5 ppm; d, ^PF = 606.0 Hz) was also identified in the 19F NMR spectrum.
EXAMPLE III:
In the following SF6 was allowed to react with a phosphine having three benzimidazolimine substituents according to the following reaction:
The NMR study to verify the degradation of sulfur hexafluoride with the phosphine was performed in THF-Ds under 1 bar SF6 pressure. After 48 h at room temperature complete conversion of phosphine could be observed. The two resonances in the 31P NMR spectrum for the phosphine sulfide (20.6 ppm) and the difluorophosphoran (-87.3 ppm; t, ^PF = 570 Hz)
verify the clean degradation of SF6 into two species. The resonance for the
difluorophosphoran (-12.8 ppm; d, ^PF = 570.0 Hz) was also identified in the 19F NMR spectrum. EXAMPLE IV:
In the following SF6 was allowed to react with an in situ formed phosphine having three pyridine-4-imine substituents according to the following reaction:
Phosphorus trichloride (0.6 mL, 6.84 mmol) was added dropwise to a stirring solution of 1- butylpyridine-4-imine (5.238 g, 34.86 mmol) in THF (50 mL) at 0 °C and the stirred reaction mixture was allowed to warm to room temperature. Conversion was monitored via 31P NMR spectroscopy from the reaction mixture. At room temperature KHMDS (4.093 g, 20.25 mmol) was added and the reaction mixture was stirred for 1 h at room temperature. The conversion was monitored via 31P NMR spectroscopy of the reaction mixture. The volatiles were removed in vacuo at 40 °C and THF (20 mL) was added to the residue. The solution was frozen in liquid nitrogen and the argon atmosphere was removed in vacuo. After warming the solution to room temperature the Schlenk-flask was pressurized with 1 bar sulfur
hexafluoride. The immediate precipitation of a yellow solid was observed. For NMR spectroscopic analysis the THF was removed in vacuo and the products were dissolved in acetonitrile. The two resonances in the 31P NMR spectrum for the phosphine sulfide (45.1 ppm) and the fluorophosphonium (15.8 ppm; t, 1JPF = 951.0 Hz) verify the clean degradation of SF6 into these two species. The resonance for the fluorophosphonium (-69.0 ppm; d, 1JPF = 951.0 Hz)
was clearly identified in the F NMR spectrum as well as the [F-D-F] anion (-149 ppm, 2/DF = 18.0 Hz).
The particular combinations of elements and features in the above detailed embodiments are exemplary only; the interchanging and substitution of these teachings with other teachings in this and the patents/applications incorporated by reference are also expressly contemplated. As those skilled in the art will recognize, variations, modifications, and other implementations of what is described herein can occur to those of ordinary skill in the art without departing from the spirit and the scope of the invention as claimed. Accordingly, the foregoing description is by way of example only and is not intended as limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage. The invention's scope is defined in the following claims and the equivalents thereto. Furthermore, reference signs used in the description and claims do not limit the scope of the invention as claimed.
Claims
C l a i m s
A method for the activation and/or degradation of SF6 is provided comprising the step of contacting SF6 with a phosphine PRXR2R3, whereby at least one of the R1 to R3 is a moiety which is has π-donating characteristics.
The method of claim 1, whereby the moiety which has π-donating
characteristics comprises a structure A-B with
with R4, R5, R8, R16 being selected independently from each other hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, alkoxy, long chain alkoxy, alkylene, aryl, arylene, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, and with R6, R7, R9 to R15 being selected independently from each other hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, alkoxy, long chain alkoxy, alkylene, aryl, arylene, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, dialkylamine, whereby two suitable substituents may form a ring, especially an aromatic ring.
The method of Claim 1 or 2, whereby the moiety which has π-donating characteristics comprises a structure A-B with
with M+ being selected from alkali and Mg-Halogenide,
R17 and R18 being selected independently from each other hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, alkoxy, long chain alkoxy, alkylene, aryl, arylene, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, dialkylamine whereby two suitable substituents may form a ring, especially an aromatic ring.
The method of any of the claims 1 to 3, whereby the moiety which has π- donating characteristics is selected out of the group comprising amido groups, carbanions, oxido group or out of the neutral groups comprising imidazol-2- ylidenamino groups, imidazolin-2-ylidenamino groups, imidazolidin-2- ylidenamino groups, benzimidazolin-2-ylidenamino groups, imidazolin-4- ylidenamino groups, imidazol-2-ylidenmethyl groups, imidazolin-2- ylidenmethyl groups, imidazolidin-2-ylidenmethyl groups, benzimidazolin-2- ylidenmethyl groups, imidazolin-4-ylidenmethyl groups, pyridine-2- ylidenamino groups, pyridine-4-ylidenamino groups, pyridine-2-ylidenmethyl groups, pyridine-4-ylidenmethyl groups, phosphoranylidenamino groups, phosphoranylidenmethyl groups and mixtures thereof.
The method of any of the claims 1 to 4, whereby the moiety which has π- donating characteristics comprises imines.
6. The method of any of the claims 1 to 5, whereby the method is carried out at a temperature between > -78°C and < 60°C.
7. The method of any of the claims 1 to 6, whereby the inventive method is
carried out in a non-protic organic solvent.
8. The method of any of the claims 1 to 7, whereby the method is carried out with the phosphine applied on a solid carrier.
9. The method of any of the claims 1 to 8, whereby the phosphine, the phosphine does not form a part of a metal complex and/or is not a ligand to a metal during the activation and/or degradation of SF6.
10. The method of any of the claims 1 to 9, whereby the phosphine does not form a part of a Rhodium complex and/or is not a ligand to Rhodium during the activation and/or degradation of SF6.
11. PR1R2R3F+ SF5 " and/or PR1R2R3F2.
12. The use of PR^R^ SF5 " and/or PR1R2R3F2 in fluorination reactions.
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