NO122412B - - Google Patents
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- NO122412B NO122412B NO164839A NO16483966A NO122412B NO 122412 B NO122412 B NO 122412B NO 164839 A NO164839 A NO 164839A NO 16483966 A NO16483966 A NO 16483966A NO 122412 B NO122412 B NO 122412B
- Authority
- NO
- Norway
- Prior art keywords
- parts
- formula
- alkyl
- compound
- phosphite
- Prior art date
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- 150000001875 compounds Chemical class 0.000 claims description 31
- -1 cycloalkyl-aralkyl Chemical group 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical group COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 5
- ZZWJQCJQAXZVOM-UHFFFAOYSA-N 2,2-dichloro-n,n-diethylacetamide Chemical compound CCN(CC)C(=O)C(Cl)Cl ZZWJQCJQAXZVOM-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003776 cleavage reaction Methods 0.000 claims description 4
- 230000007017 scission Effects 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 230000000749 insecticidal effect Effects 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- PBGGNZZGJIKBMJ-UHFFFAOYSA-N di(propan-2-yl)azanide Chemical compound CC(C)[N-]C(C)C PBGGNZZGJIKBMJ-UHFFFAOYSA-N 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 238000009835 boiling Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 7
- 229960003750 ethyl chloride Drugs 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- CQQUWTMMFMJEFE-UHFFFAOYSA-N 2-chloro-n,n-diethylacetamide Chemical compound CCN(CC)C(=O)CCl CQQUWTMMFMJEFE-UHFFFAOYSA-N 0.000 description 4
- DSFYLUWONYJGRI-UHFFFAOYSA-N 4,4-dichloro-N,N-diethyl-3-oxobutanamide Chemical compound C(C)N(C(CC(=O)C(Cl)Cl)=O)CC DSFYLUWONYJGRI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical class CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- NTMXFHGYWJIAAE-UHFFFAOYSA-N n,n-diethyl-3-oxobutanamide Chemical compound CCN(CC)C(=O)CC(C)=O NTMXFHGYWJIAAE-UHFFFAOYSA-N 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 2
- FGCTYLRDRKTVRR-UHFFFAOYSA-N 4,4-dichloro-3-oxobutanamide Chemical compound NC(=O)CC(=O)C(Cl)Cl FGCTYLRDRKTVRR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- PKUWKAXTAVNIJR-UHFFFAOYSA-N O,O-diethyl hydrogen thiophosphate Chemical group CCOP(O)(=S)OCC PKUWKAXTAVNIJR-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical class CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical class COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- WUFFGJVXZCDALE-UHFFFAOYSA-N 2-ethoxy-1,3,2-dioxaphospholane Chemical compound CCOP1OCCO1 WUFFGJVXZCDALE-UHFFFAOYSA-N 0.000 description 1
- GRZZTYUZNNKOFW-UHFFFAOYSA-N 2-hydroxy-1,3,2-dioxaphospholane Chemical group OP1OCCO1 GRZZTYUZNNKOFW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- VHYHDIMRASAICZ-UHFFFAOYSA-N CCCCCCCCCCCCOP(O)OCC Chemical class CCCCCCCCCCCCOP(O)OCC VHYHDIMRASAICZ-UHFFFAOYSA-N 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical class CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- XWFQVJWIUPRIFF-UHFFFAOYSA-N benzyl ethyl hydrogen phosphite Chemical class CCOP(O)OCC1=CC=CC=C1 XWFQVJWIUPRIFF-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- UXZAVIKBXUIYGV-UHFFFAOYSA-N cyclohexyl diethyl phosphite Chemical compound CCOP(OCC)OC1CCCCC1 UXZAVIKBXUIYGV-UHFFFAOYSA-N 0.000 description 1
- CLNAKAMERQATIK-UHFFFAOYSA-N cyclohexyl methyl hydrogen phosphite Chemical class COP(O)OC1CCCCC1 CLNAKAMERQATIK-UHFFFAOYSA-N 0.000 description 1
- VSOOIPBBIVYJID-UHFFFAOYSA-N dibenzyl propyl phosphite Chemical compound P(OCC1=CC=CC=C1)(OCC1=CC=CC=C1)OCCC VSOOIPBBIVYJID-UHFFFAOYSA-N 0.000 description 1
- DMDSLMWVIMKDQA-UHFFFAOYSA-N diethoxy(ethylsulfanyl)phosphane Chemical compound CCOP(OCC)SCC DMDSLMWVIMKDQA-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- ILXZMTJXXHNZJS-UHFFFAOYSA-N diethyl hydrogen phosphate;hydrochloride Chemical compound Cl.CCOP(O)(=O)OCC ILXZMTJXXHNZJS-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NXWXWGADJYEOIK-UHFFFAOYSA-N dimethyl oxolan-2-ylmethyl phosphite Chemical compound COP(OC)OCC1CCCO1 NXWXWGADJYEOIK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MKKAUEQFHRQREG-UHFFFAOYSA-N ethyl oxolan-2-ylmethyl hydrogen phosphite Chemical class CCOP(O)OCC1CCCO1 MKKAUEQFHRQREG-UHFFFAOYSA-N 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 description 1
- LUVCTYHBTXSAMX-UHFFFAOYSA-N tris(2-chloroethyl) phosphite Chemical compound ClCCOP(OCCCl)OCCCl LUVCTYHBTXSAMX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Optical Elements Other Than Lenses (AREA)
Description
Fremgangsmåte til fremstilling av nye organiske fosforforbindelser med insektisid virkning. Process for the production of new organic phosphorus compounds with insecticidal action.
Foreliggende oppfinnelse angår nye The present invention relates to new
organiske forbindelser med den generelle organic compounds with the general
formel formula
hvori R, Ri, R3 og R4 betyr alkyl-, cyklo- in which R, R 1 , R 3 and R 4 mean alkyl-, cyclo-
alkyl-, aralkyl-, arylrester eller tetrahydro- alkyl, aralkyl, aryl residues or tetrahydro-
furylresten, idet R og Ri sammen med X the furyl residue, wherein R and Ri together with X
og P kan danne en ring og Rh og Ri sammen med N kan danne en ring, eventuelt en morfolinring, videre kan R.s og R4 også be- and P can form a ring and Rh and Ri together with N can form a ring, possibly a morpholine ring, furthermore R.s and R4 can also be
ty vannstoff, R2 bety vannstoff, en alkyl- means hydrogen, R2 means hydrogen, an alkyl-
rest eller et halogenatom, Rs bety en alkyl-, residue or a halogen atom, Rs means an alkyl-,
aryl- eller furfurylrest, X betyr -O- eller aryl or furfuryl residue, X means -O- or
-S-. Hvilke av formlene I eller II som skal tildeles forbindelsene ifølge oppfinnelsen kunne hittil ikke avgjøres med sikkerhet. -S-. Which of the formulas I or II should are assigned to the compounds according to the invention could not so far be determined with certainty.
Muligvis oppstår alt etter fremstillings- Possibly everything occurs after manufacturing
måten bare den ene eller bare den annen form, eller den ene oppstår som foretruk- the way only one or only the other form, or one occurs as preferred
ket. Det er kjent at ved Michaelis-Arbuzow ket. It is known that at Michaelis-Arbuzow
-reaksjonen av trialkyl-fosfitter opptrer -the reaction of trialkyl phosphites occurs
det omleiringer med visse halogenforbin- rearrangements with certain halogen compounds
delser, således at i stedet for det ventede fosfonsyrederivat oppstår det isomere fos- parts, so that instead of the expected phosphonic acid derivative, the isomeric phos-
forsyreestere. I tilfelle av foreliggende opp- acid esters. In the case of the present up-
finnelse, kan f. eks. kondensasjonsproduk- invention, can e.g. condensation product
tet av a,a-dikloraceteddiksyre-N-dietyl- ted by α,α-dichloroacetacetic acid-N-diethyl-
amid og trimetylfosfitt formuleres på føl- amide and trimethylphosphite are formulated on
gende måter: gende ways:
Foreliggende oppfinnelse omfatter der-for fremstilling av forbindelser med formlene (I) og (II) samt deres blandinger da isomerien for forbindelsene kan oppfattes som keto-enol-tautomerie. Når i det føl-gende bare den ene form angis, så skal all-tid også den annen form tas i betraktning, såfremt den synes eksistensberettiget. The present invention therefore encompasses the production of compounds with the formulas (I) and (II) as well as their mixtures, as the isomerism for the compounds can be perceived as keto-enol tautomerism. When in the following only one form is indicated, the other form must always also be taken into account, provided that it seems justified to exist.
De nye forbindelser er verdifulle midler The new connections are valuable resources
til bekjempelse av skadevesener, særlig ani-malske. De virker på deres forskjellige ut-viklingstrinn, slik som egg, larver, imagines, idet en virkning som kontakt- og spisegift kommer i betraktning. Egnede substituerte forbindelser oppviser anvendt ved planter, indreterapeutiske såkalte systemiske virk-ninger. Særlig verdifulle er forbindelser med den generelle formel for combating pests, especially animals. They act on their various stages of development, such as eggs, larvae, imagines, taking into account an effect as a contact and food poison. Suitable substituted compounds exhibit internal therapeutic so-called systemic effects when used in plants. Particularly valuable are compounds with the general formula
hvori R, Ri betyr laveremolekylare alkyl - rester med 1—4 kullstoffatomer, og Rs og R.; vannstoff eller likeledes laveremolekylare alkylrester med 1—4 kullstoffatomer. hvori R, Ri og X har den ovenfor angitte betydning og Rn betyr en laveremolekylar alkylrest med 1 til 4 kullstoffatomer med en forbindelse med formelen hvori Ri>, Rs, R4 og Rs har den ovenfor angitte betydning og hal betyr et halogenatom, slik som brom eller fortrinsvis klor under avspaltning av en forbindelse R7-hal. Forbindelsene ifølge oppfinnelsen kan fåes ved hjelp av kondensasjon av en forbindelse med formelen De nye produkter kan også fremstilles ved omsetning av en forbindelse med formelen hvori R, Ri og X har den ovenfor angitte betydning og Me betyr et alkalimetall, fortrinsvis natrium, med en slik formel hvori R.2, R3, R4, R5 og hal har den ovenfor angitte betydning. For fremstilling av forbindelser, hvori R2 betyr vannstoff eller en alkylrest, kan også følgende kondensasjon utføres: wherein R, Ri mean lower molecular weight alkyl residues with 1-4 carbon atoms, and Rs and R.; hydrogen or likewise lower molecular weight alkyl residues with 1-4 carbon atoms. wherein R, Ri and X have the above meaning and Rn means a lower molecular weight alkyl radical of 1 to 4 carbon atoms with a compound of the formula wherein Ri>, Rs, R4 and Rs have the above meaning and hal means a halogen atom, such as bromine or preferably chlorine during cleavage of a compound R7-hal. The compounds according to the invention can be obtained by condensation of a compound with the formula The new products can also be prepared by reacting a compound with the formula in which R, Ri and X have the above meaning and Me means an alkali metal, preferably sodium, with such formula in which R.2, R3, R4, R5 and hal have the meaning given above. For the preparation of compounds, in which R2 means hydrogen or an alkyl residue, the following condensation can also be carried out:
Hvilke av de anførte reaksjoner som velges avhenger av utgangsmaterialenes tilgjen-gelighet. Which of the listed reactions is chosen depends on the availability of the starting materials.
De som utgangsmaterialer benyttbare forbindelser med den generelle formel The compounds with the general formula that can be used as starting materials
avledes av treverdig fosfor, mens produktene som fremstilles ved hjelp av frem-gangsmåten er derivater av det 5-verdige fosfor. Blant forbindelsene med den nettopp anførte formel er slike, hvori symbolene X, Y og Z betyr surstoff, lettest tilgjengelig, De tilsvarer den generelle formel og kan fremstilles etter kjente fremgangs-måter. De alifatiske rester, som er vist ved symbolene R og Ri kan være uforgrenet, forgrenet, mettet eller umettet. Det kan nevnes f. eks. følgende grupper: Metyl-, etyl-, propyl-, isopropyl-, butyl-, heksyl-, 2-etylbutyl-, oktyl-, 2-butyl-oktyl-, lauryl-, oktadecyl-, allyl-, 2-kloretyl-; videre radikaler med rhodan-, cyan- eller estergrupper. Restene R og Ri kan være de samme eller forskjellige. Ro er fortrinsvis en laveremolekylar alkylrest med 1—4 kullstoffatomer. F. eks. skal følgende forbindelser nevnes: Trimetylfosfitt, trietylfosfitt, tri-propylfosfitt, -dietyl-laurylfosfitt, tri-(2-klor-etyl)-fosfitt eller ester med formelen De aromatiske radikaler, som er vist ved R og Ri kan være en- eller flerkjernet, og kan eventuelt også ha kjernesubstitu-enter. Det skal nevnes fenyl-, 2- eller 4-klorfenyl-, 2,4-diklorfenyl-, 4-metoksy-fenyl-, 4-nitrofenyl-, naftyl- eller 4-difenyl -rester, forbindelser slik som 2,4-diklorfenyl-dietylfosfitt eller 4-klorfenyl-dimetyl-fosfitt. Blant de aralifatiske radikaler som vist ved R og Ri skal nevnes benzyl-, under de cykloalifatiske radikaler cyklo-heksyl- og under de heterocykliske radikaler tetra-hydrofurfurylrester. Utgangsmaterialene med slike rester er f. eks. cykloheksyl-dietyl -fosfitt, tetrahydro-furfuryl-dimetylfosfitt eller dibenzyl-propylfosfitt. Blant forbindelsene, hvori X og Y betyr svovel, skal nevnes trietyltiofosfitt med formelenForbindelsene med den generelle formel er salter av disubstituerte fosfitter eller fosfinsyrer, slik som f. eks. natriumsalter av dimetylfosfitt, dietylfo.sfitt, lauryletyl-fosfitt, cykloheksylmetylfosfitt, tetrahydro-furfuryletylfosfitt eller benzyletylfosfitt. Forbindelsene med den generelle formel er fosforsyre-monohalogenider, slik som f. eks. fosforsyre-dietylestermonoklorid, tio-fosforsyre-dietylester-monoklorid. Forbindelsene med den generelle formel is derived from trivalent phosphorus, while the products produced using the method are derivatives of the 5-valent phosphorus. Among the compounds with the formula just stated, those in which the symbols X, Y and Z mean oxygen are the most readily available. They correspond to the general formula and can be prepared according to known methods. The aliphatic residues, which are shown by the symbols R and Ri can be unbranched, branched, saturated or unsaturated. It can be mentioned e.g. the following groups: Methyl-, ethyl-, propyl-, isopropyl-, butyl-, hexyl-, 2-ethylbutyl-, octyl-, 2-butyl-octyl-, lauryl-, octadecyl-, allyl-, 2-chloroethyl-; further radicals with rhodan, cyan or ester groups. The residues R and Ri may be the same or different. Ro is preferably a lower molecular alkyl residue with 1-4 carbon atoms. For example the following compounds should be mentioned: Trimethyl phosphite, triethyl phosphite, tri-propyl phosphite, -diethyl-lauryl phosphite, tri-(2-chloro-ethyl)-phosphite or ester with the formula The aromatic radicals, which are shown by R and Ri can be mononuclear or polynuclear , and may optionally also have core substituents. Mention must be made of phenyl, 2- or 4-chlorophenyl, 2,4-dichlorophenyl, 4-methoxy-phenyl, 4-nitrophenyl, naphthyl or 4-diphenyl residues, compounds such as 2,4-dichlorophenyl -diethyl phosphite or 4-chlorophenyl-dimethyl-phosphite. Among the araliphatic radicals as shown by R and Ri should be mentioned benzyl, among the cycloaliphatic radicals cyclohexyl and among the heterocyclic radicals tetrahydrofurfuryl residues. The starting materials with such residues are e.g. cyclohexyl diethyl phosphite, tetrahydrofurfuryl dimethyl phosphite or dibenzyl propyl phosphite. Among the compounds, in which X and Y represent sulfur, mention should be made of triethylthiophosphite with the formula The compounds with the general formula are salts of disubstituted phosphites or phosphinic acids, such as e.g. sodium salts of dimethyl phosphite, diethyl phosphite, lauryl ethyl phosphite, cyclohexyl methyl phosphite, tetrahydrofurfuryl ethyl phosphite or benzyl ethyl phosphite. The compounds with the general formula are phosphoric acid monohalides, such as e.g. phosphoric acid diethyl ester monochloride, thiophosphoric acid diethyl ester monochloride. The compounds with the general formula
er amider av halogenert aceteddiksyre. Restene Rs og Ri kan ha den videre ovenfor for restene R og Ri angitte betydning. Fortrinsvis betyr de laveremolekylare alkyl-grupper med 1—4 kullstoffatomer eller danner ledd i en heterocyklisk ring, f. eks. morfolin eller piperidin. are amides of halogenated acetoacetic acid. The residues Rs and Ri can have the meaning stated further above for the residues R and Ri. Preferably, they mean lower molecular weight alkyl groups with 1-4 carbon atoms or form links in a heterocyclic ring, e.g. morpholine or piperidine.
Resten R2 kan bety et halogenatom, fortrinnsvis et kloratom, et vannstoffatom eller en alkylrest med fortrinsvis 1—4 kullstoffatomer, slik som metylresten. R5 kan være en furfurylrest, en arylrest, f. eks. fenyl-, klorfenyl-, nitrofenyl-resten eller særlig en alkylrest med 1—4 kullstoffatomer. Resten R„ er fortrinsvis en metyl-gruppe. The radical R2 can mean a halogen atom, preferably a chlorine atom, a hydrogen atom or an alkyl radical with preferably 1-4 carbon atoms, such as the methyl radical. R5 can be a furfuryl residue, an aryl residue, e.g. the phenyl, chlorophenyl, nitrophenyl residue or in particular an alkyl residue with 1-4 carbon atoms. The residue R„ is preferably a methyl group.
For fremstilling av produktene ifølge oppfinnelsen opphetes reaksjon.skomponen-tene til høyere temperatur, f. eks. 50 til 200° C, og fortrinsvis ca. 90 til 150° C. Det kan være fordelaktig eller hensiktsmessig å anvende inerte oppløsningsmidler, slik som benzol, toluol, xylol, klorbenzen eller bensin og eventuelt arbeide i en inert gass-atmosfære, f. eks. under kvelstoff og/under forminsket trykk. For the production of the products according to the invention, the reaction components are heated to a higher temperature, e.g. 50 to 200° C, and preferably approx. 90 to 150° C. It may be advantageous or appropriate to use inert solvents, such as benzene, toluene, xylol, chlorobenzene or petrol and possibly work in an inert gas atmosphere, e.g. under nitrogen and/under reduced pressure.
I det norske patent nr. 80.467 er det beskrevet midler til bekjempelse av skade-dyr, hvilke fåes ved omsetning av et fos-fat eller tiofosfat med halogeneddiksyre-amider. Likeoverfor disse forbindelser ad-skiller forbindelsene ifølge foreliggende oppfinnelse seg ved at det anvendes halogenerte aceteddiksyreamider, hvorved det oppstår andre forbindelser. In Norwegian patent no. 80,467, agents for combating pests are described, which are obtained by reacting a phosphate or thiophosphate with haloacetic acid amides. Directly opposite these compounds, the compounds according to the present invention differ in that halogenated acetoacetic acid amides are used, whereby other compounds are formed.
I det norske patent nr. 80.467 er det beskrevet forbindelser med den generelle formel In the Norwegian patent no. 80,467, compounds with the general formula are described
som insektisider, idet Ri og R2 betyr alkyl, | as insecticides, wherein R1 and R2 mean alkyl, |
aralkyl eller aryl, R3 og R4 betyr vannstoff - atomer eller alkyl, oksyalkyl eller arylrester, Xi, Xa og Xs betyr surstoff eller svovel og m betyr et lite tall. aralkyl or aryl, R3 and R4 mean hydrogen atoms or alkyl, oxyalkyl or aryl residues, Xi, Xa and Xs mean oxygen or sulfur and m means a small number.
Disse kjente forbindelser er sterkt un-derlegne i forhold til de sammenlignbare forbindelser ifølge oppfinnelsen med hen-syn til virkningen mot bladlus, og som kon-taktinsektisider, samt systemisk og i diffu-sjonsprøven. These known compounds are greatly inferior to the comparable compounds according to the invention with regard to the effect against aphids, and as contact insecticides, as well as systemically and in the diffusion test.
I de følgende eksempler betyr deler vektsdeler. Forholdet mellom vektsdel og volumdel er det samme som mellom kilo-gram og liter. Temperaturene er angitt i Celciusgrader. In the following examples, parts means parts by weight. The ratio between weight part and volume part is the same as between kilogram and liter. The temperatures are indicated in degrees Celsius.
Eksempel 1. Example 1.
11,3 deler dikloraceteddiksyredietylamid (Kp(U8 92,5 — 93° C) og 8,3 deler trietylfosfitt blandes sammen ved rom-temperatur. For innledning av reaksjonen oppvarmes blandingen til 90° C. Med denne temperatur begynner en kraftig gass-utvikling og reaksjonsoppløsningen opphetes uten ytre varmetilførsel til 160° C. Etter avsluttet reaksjon evakueres produktet ennå kort tid i vannstrålevakuum ved 95° C. Det blir tilbake en rød-grønnskimrende olje (16,1 deler) som kan renses ved hjelp av høyvakuumdestillasjon. Kp. 0,1 mm Hg 144° C. 11.3 parts of dichloroacetic acid diethylamide (Kp(U8 92.5 — 93° C) and 8.3 parts of triethyl phosphite are mixed together at room temperature. To start the reaction, the mixture is heated to 90° C. At this temperature, a strong gas evolution begins and the reaction solution is heated without external heat supply to 160° C. After the reaction has finished, the product is evacuated for a short time in a water jet vacuum at 95° C. A red-green shimmering oil (16.1 parts) remains which can be purified using high vacuum distillation. 0.1 mm Hg 144° C.
C12H23OSNCIP C12H23OSNCIP
Beregnet: N 4,27% Cl 10,82%. Funnet: N 4,24% Cl 10,97%. Calculated: N 4.27% Cl 10.82%. Found: N 4.24% Cl 10.97%.
Det dikloraceteddiksyredietylamid som ble anvendt til fremstilling av dette kon-densasjonsprodukt, lar seg fremstille ved klorering av aceteddiksyredietylamid med 2 mol sulfurylklorid. The dichloroacetoacetic acid diethylamide which was used to prepare this condensation product can be prepared by chlorination of acetoacetic acid diethylamide with 2 mol of sulfuryl chloride.
Ekseynpel 2. Example 2.
En blanding av 33,8 deler dikloraceteddiksyredietylamid og 34 deler klorbenzol opphetes til kokning. Man lar innen 5 minutter 20,5 deler trimetylfosfitt dryppe til. Det begynner en heftig gass-utvikling som er avsluttet etter en times kokning under tilbakeløpskjøling. I vannstrålevakuum fjerner man de lett flyktige deler og klorbenzol og får som rest 45,0 deler av en orangefarget olje, som lar seg destillere i høyvakuum. Kokep.nl 138 — 142° C (37,2 deler = 82,6% av det teoretiske). CioHmOoNClP A mixture of 33.8 parts of dichloroacetoacetic acid diethylamide and 34 parts of chlorobenzene is heated to boiling. Within 5 minutes, 20.5 parts of trimethylphosphite are added. Violent gas development begins, which is finished after an hour of boiling under reflux cooling. In a water jet vacuum, the easily volatile parts and chlorobenzene are removed and the residue is 45.0 parts of an orange-coloured oil, which can be distilled under high vacuum. Kokep.nl 138 — 142° C (37.2 parts = 82.6% of the theoretical). CioHmOoNClP
Beregnet: C 40,07 % H 6,39% Calculated: C 40.07% H 6.39%
N 4,67 % Cl 11,83 % N 4.67% Cl 11.83%
P 10,34%. P 10.34%.
Funnet: C 39,90 % H 6,61 % Found: C 39.90% H 6.61%
N 4,70 % Cl 11,78 % N 4.70% Cl 11.78%
P 10,38%. P 10.38%.
Eksempel 3. Example 3.
9,6 deler monokloraceteddiksyredietyl-amid (kokepunkt 0 v> 83,85° C) oppvarmes til 120° C. Dertil drypper man 8,3 deler trietylfosfitt. Temperaturen i reaksjons-blandingen stiger til 155° C og det unnviker etylklorid. Etter avsluttet tildrypping opphetes blandingen ennå så lenge til 150° C, inntil gassutviklingen opphører, hvilket er etilfellet etter 15 minutter. Deretter fjernes de siste rester av lettflyktige deler ved vannstrålevakuum. Som rest ble det tilbake 14,0 deler av en lys orangefarget olje, som er lett oppløselig i eter, aceton og alkohol. 9.6 parts of monochloroacetic acid diethyl amide (boiling point 0 v> 83.85° C) are heated to 120° C. 8.3 parts of triethyl phosphite are added drop by drop. The temperature in the reaction mixture rises to 155° C and ethyl chloride escapes. After completion of the dripping, the mixture is further heated to 150° C, until gas evolution ceases, which is the ethyl trap after 15 minutes. The last remnants of easily volatile parts are then removed by water jet vacuum. As a residue, 14.0 parts of a light orange colored oil, which is easily soluble in ether, acetone and alcohol, remained.
Det her anvendte monokloraceteddik-syredietylamid kan fremstilles ved innvirk-ning av 1 mol sulfurylklorid på aceteddiksyredietylamid. The monochloroacetic acid diethylamide used here can be prepared by the action of 1 mol of sulfuryl chloride on acetoacetic acid diethylamide.
Eksempel 4. Example 4.
Til 9,6 deler monokloraceteddiksyredi-etylamid, som er opphetet til 140° C, lar man 6,2 deler trimetylfosfitt dryppe til, hvorved inntrer en livlig gassutvikling og temperaturen økes til 140—150° C. Reaksjonen føres til slutt ved hjelp av varme-tilførsel utvendig fra ved 150° C. Etter kort evakuering ved 95° C blir det tilbake 12,45 deler mørkerød olje, som kan renses ved hjelp av høyvakuumdestillasjon. Kokepunkt 0,15 143° C. To 9.6 parts of monochloroacetic acid diethylamide, which has been heated to 140° C, 6.2 parts of trimethyl phosphite are allowed to drip, whereby a lively evolution of gas occurs and the temperature is increased to 140-150° C. The reaction is finally carried out with the aid of heat - external supply from at 150° C. After brief evacuation at 95° C, 12.45 parts of dark red oil remain, which can be purified using high vacuum distillation. Boiling point 0.15 143° C.
C0H20O5NP C0H20O5NP
Beregnet: N 5,28% P 11,68%. Funnet: N 5,14 % P 11,53 %. Calculated: N 5.28% P 11.68%. Found: N 5.14% P 11.53%.
Produktet er godt oppløselig i aceton og alkohol, mindre godt oppløselig i eter. The product is well soluble in acetone and alcohol, less well soluble in ether.
Eksempel 5. Example 5.
8,5 deler dikloraceteddiksyreamid (smeltepunkt 65° C) dekkes med 20 volumdeler xylol. Blandingen opphetes til 90° C og tilsettes dråpevis 8,3 deler trietylfosfitt. Temperaturen holder seg uten utvendig opphetning ved 110—120° C, og fra reak-sjonsblandingen unnviker etylklorid. Deretter fjerner man oppløsningsmidlet i vakuum ved 95° C. Som rest blir det tilbake 13,6 deler av en rødlig, grønn opaliserende olje. Produktet er godt oppløselig i aceton og alkohol, mindre godt oppløselig i eter. Dikloraceteddiksyreamid lar seg fremstille av aceteddiksyreamid ved klorering i kloroform med 2 mol sulfurylklorid. 8.5 parts of dichloroacetoacetic acid amide (melting point 65° C) are covered with 20 parts by volume of xylol. The mixture is heated to 90° C and 8.3 parts of triethyl phosphite are added dropwise. The temperature remains at 110-120° C without external heating, and ethyl chloride escapes from the reaction mixture. The solvent is then removed in a vacuum at 95° C. As a residue, 13.6 parts of a reddish, green opalescent oil remain. The product is well soluble in acetone and alcohol, less well soluble in ether. Dichloroacetoacetic acid amide can be prepared from acetoacetic acid amide by chlorination in chloroform with 2 moles of sulfuryl chloride.
Eksempel 6. Example 6.
En blanding av 8,5 deler dikloraceteddiksyreamid og 20 volumdeler xylol som er blitt oppvarmet til 90—100° C tilsettes lang-somt 6,2 deler trimetylfosfitt, således at temperaturen uten opphetning holder seg ved 110—120° C. Etter at gassutviklingen opphører, fjernes xylolen i vannstrålevakuum ved 95° C badtemperatur. Reaksjons-produktet er en rødlig, grønnskimrende olje (11,5 deler) og godt oppløselig i aceton og alkohol. A mixture of 8.5 parts of dichloroacetacetic acid amide and 20 parts by volume of xylol which has been heated to 90-100° C is slowly added to 6.2 parts of trimethylphosphite, so that the temperature without heating remains at 110-120° C. After gas evolution ceases , the xylene is removed in a water jet vacuum at 95° C bath temperature. The reaction product is a reddish, green shimmering oil (11.5 parts) and well soluble in acetone and alcohol.
På analog måte kan de i følgende tabell oppstillede halogenerte (3-ketosyreamider omsettes med tertiære fosfitter. De danne-de estere, hvis beskaffenhet likeledes er angitt i tabellen, er bare delvis uspaltet destillerbare i høyvakuum. For fremstilling av bekjempelsesmidler for skadevesener er det dog tilstrekkelig med en rensing av forbindelsene ved destillasjon. In an analogous way, the halogenated (3-keto acid amides listed in the following table can be reacted with tertiary phosphites. The formed esters, whose nature is also indicated in the table, are only partially uncleaved distillable in high vacuum. For the production of pest control agents, however, it is sufficient with a purification of the compounds by distillation.
Eksempel 7. Example 7.
11,3 deler dikloraceteddiksyredietylamid opphetes i 15 volumdeler xylol til kokning og blandingen tilsettes innen 5 minutter 12,2 deler dietyltetrahyrofurfuryl- 11.3 parts of dichloroacetoacetic acid diethylamide are heated in 15 parts by volume of xylol to boiling and the mixture is added within 5 minutes 12.2 parts of diethyltetrahydrofurfuryl-
C). For å avslutte reaksjonen holdes blandingen ennå 1 time ved koketemperatur. Det avdestillerer 2,5 deler etylklorid. Man fjerner xylolen i vakuum og litt tilstede-værende utgangsmateriale i høyvakuum ved 180—190° badtemperatur. Som rest blir det tilbake 14,9 deler lys olje, som oppløser seg meget godt i aceton og alkohol, og mindre godt i vann. C). To terminate the reaction, the mixture is kept for a further 1 hour at boiling temperature. It distills off 2.5 parts of ethyl chloride. The xylene is removed in a vacuum and some starting material present in a high vacuum at 180-190° bath temperature. As a residue, 14.9 parts of a light oil remain, which dissolves very well in acetone and alcohol, and less well in water.
På analog måte omsettes følgende fosfitter med dikloraceteddiksyredietylamid: In an analogous way, the following phosphites are reacted with dichloroacetoacetic acid diethylamide:
Eksempel 8. Example 8.
Man oppvarmer 11,3 deler dikloraceteddiksyredietylamid til 150° C og tildrypper innen 5 minutter 7,5 deler etyl-etylenfosfitt. 11.3 parts of dichloroacetic acid diethylamide are heated to 150° C and 7.5 parts of ethyl-ethylene phosphite are added dropwise within 5 minutes.
Man holder blandingen ennå i ly^ time ved 160° C inntil avslutning av etylkloridutviklingen. Det avspaltes 1,2 deler etylklorid. Reaksjonen forløper ikke ensartet under avspaltning av etylklorid, men foregår også delvis under oppspaltning av etylenfosfitt-ringen. Man fjerner i'høyvakuum ennå til-stedeværende utgangsmaterialer ved en badtemperatur på 180° C og får som rest en seigtflytende olje (10,8 deler), som er godt oppløselig i alkohol og aceton og mindre godt oppløselig vann. The mixture is kept for a further 1 hour at 160° C until the end of the evolution of ethyl chloride. 1.2 parts of ethyl chloride are split off. The reaction does not proceed uniformly during cleavage of ethyl chloride, but also takes place partially during cleavage of the ethylene phosphite ring. Starting materials still present are removed in high vacuum at a bath temperature of 180° C. The residue is a viscous oil (10.8 parts), which is well soluble in alcohol and acetone and less well soluble in water.
Eksempel 9. Example 9.
11,3 deler dikloraceteddiksyredietylamid oppvarmes til 180° C. Man tildrypper i løpet av 5 minutter 11,7 deler tritioetylfos-fitt (C2Hr,S).sP og lar etylkloridutviklingen avslutte i løpet av y4 time ved 180° C. Man fjerner i høyvakuum ved 150° C tilstede-værende utgangsmaterialer og får som rest en seig masse (17,6 deler), som er lett opp-løselig i kloroform, mindre godt oppløselig i alkohol og aceton. 11.3 parts of dichloroacetic acid diethylamide are heated to 180° C. 11.7 parts of trithioethyl phosphite (C2Hr,S).sP are added dropwise over the course of 5 minutes and the evolution of ethyl chloride is allowed to end within 4 hours at 180° C. It is removed under high vacuum at 150° C. starting materials present and as a residue a tough mass (17.6 parts) is obtained, which is easily soluble in chloroform, less soluble in alcohol and acetone.
Eksempel 10. Example 10.
13,8 deler dietylfosfitt dryppes til en opslemning av 2,3 deler natriumstykker i 13.8 parts of diethyl phosphite are dropped into a slurry of 2.3 parts of sodium pieces in
70 volumdeler eter. Så snart alt natrium 70 parts by volume of ether. As soon as all sodium
er gått i oppløsning, tilsetter man dråpevis en blanding av 20,6 deler a-klor-a-metylaceteddiksyredietylamid (kp0 15 87° C) og 30 volumdeler eter ved 20—30° C. Man has dissolved, a mixture of 20.6 parts of a-chloro-a-methylacetoacetic acid diethylamide (bp 15 87° C) and 30 parts by volume of ether at 20-30° C is added dropwise.
oppheter ennå 6 timer til kokning under tilbakeløpskjøling og etter avkjøling vasker man ut koksaltet med litt vann. Eteropp-løsnningen tørkes over natriumsulfat, ete-ren avdestilleres, og resten (22,6 deler) destilleres i høyvakuum. Man får 13,7 deler av en gulaktig olje med kokepunkt 015 141 —148° C. reheat for a further 6 hours until boiling under reflux cooling and after cooling wash out the coking salt with a little water. The ether solution is dried over sodium sulfate, the ether is distilled off, and the residue (22.6 parts) is distilled under high vacuum. You get 13.7 parts of a yellowish oil with a boiling point of 015 141 -148° C.
C]3H2«05NP C]3H2«O5NP
På samme måte omsettes natriumsaltet av dietylfosfitt med a-kloraceteddik-syredietylamid til en forbindelse med bruttoformelen C12H24O5NP med kokepunkt 0,2 132° C. In the same way, the sodium salt of diethyl phosphite is reacted with α-chloroacetic acid diethylamide to a compound with the gross formula C12H24O5NP with a boiling point of 0.2 132° C.
På analog måte kan også natriumsaltet av dimetylfosfitt omsettes med <x-kloraceteddiksyredietylamid. In an analogous manner, the sodium salt of dimethyl phosphite can also be reacted with <x-chloroacetic acid diethylamide.
Eksempel 11. Example 11.
En oppslemning av 2,3 deler natriumstykker i 200 volumdeler dioksan tilsettes ved 50—60° C dråpevis 17,3 deler aceteddiksyredietylamid. Natriumet går i løpet av A slurry of 2.3 parts of sodium pieces in 200 parts by volume of dioxane is added dropwise at 50-60° C. 17.3 parts of acetoacetic acid diethylamide. The sodium goes during the
2 timer under vannstoffutvikling i oppløs-ning. Man avkjøler oppløsningen av natriumsaltet til 35° C og lar 18,9 deler dietyl-tiofosforsyreesterklorid dryppe til under 2 hours during hydrogen evolution in solution. The solution of the sodium salt is cooled to 35° C and 18.9 parts of diethyl thiophosphoric acid ester chloride are allowed to drip to below
omrøring. Oppløsningen røres ennå i iy2stirring. The solution is still stirred for iy2
time ved 45° C. Etter denne tid er koksalt-utskillingen avsluttet. Man filtrerer blandingen og avdestillerer oppløsningsmidlet i hour at 45° C. After this time, the sodium chloride excretion has ended. The mixture is filtered and the solvent is distilled off
vannstrålevakuum. Det blir tilbake 32,4 water jet vacuum. That leaves 32.4
deler av en lett flytende olje, som oppløses parts of a light liquid oil, which dissolves
lett i alkohol og aceton og er ikke destiller-bar i høyvakuum. easily in alcohol and acetone and is not distillable in high vacuum.
På analog måte omsettes natriumsaltet The sodium salt is reacted in an analogous way
av a-metylaceteddiksyredietylamid (kp.on8of a-methylacetoacetic acid diethylamide (kp.on8
87° C) med dietylfosforsyreesterklorid til 87° C) with diethyl phosphoric acid ester chloride to
forbindelsen med bruttoformelen the connection with the gross formula
C13H20O5NP. Kp01 136—138° C. C13H20O5NP. Kp01 136—138° C.
Claims (3)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US49096365A | 1965-09-28 | 1965-09-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
NO122412B true NO122412B (en) | 1971-06-28 |
Family
ID=23950244
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO164839A NO122412B (en) | 1965-09-28 | 1966-09-22 |
Country Status (5)
Country | Link |
---|---|
BE (1) | BE687495A (en) |
CH (1) | CH454771A (en) |
DE (1) | DE1497286A1 (en) |
GB (1) | GB1142888A (en) |
NO (1) | NO122412B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2604921C3 (en) * | 1976-02-09 | 1984-03-08 | W.C. Heraeus Gmbh, 6450 Hanau | Lighting devices for medical or dental purposes |
GB2229264A (en) * | 1989-03-16 | 1990-09-19 | Toshiba Lighting & Technology | Lighting fixture |
DE3909246A1 (en) * | 1989-03-21 | 1990-09-27 | Leybold Ag | HEATING DEVICE FOR COOKING FOOD, ESPECIALLY HOT PLATE |
JPH0760603B2 (en) * | 1989-07-19 | 1995-06-28 | 株式会社小糸製作所 | Vehicle headlights |
-
1966
- 1966-08-26 GB GB38461/66A patent/GB1142888A/en not_active Expired
- 1966-09-16 CH CH1339466A patent/CH454771A/en unknown
- 1966-09-22 NO NO164839A patent/NO122412B/no unknown
- 1966-09-27 DE DE19661497286 patent/DE1497286A1/en active Pending
- 1966-09-28 BE BE687495D patent/BE687495A/xx unknown
Also Published As
Publication number | Publication date |
---|---|
GB1142888A (en) | 1969-02-12 |
DE1497286A1 (en) | 1969-07-17 |
CH454771A (en) | 1968-04-30 |
BE687495A (en) | 1967-03-01 |
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