GB2210367A - Preparation of N-aralkylated and N-aryloxyalkylated aminofluoranes - Google Patents
Preparation of N-aralkylated and N-aryloxyalkylated aminofluoranes Download PDFInfo
- Publication number
- GB2210367A GB2210367A GB8822146A GB8822146A GB2210367A GB 2210367 A GB2210367 A GB 2210367A GB 8822146 A GB8822146 A GB 8822146A GB 8822146 A GB8822146 A GB 8822146A GB 2210367 A GB2210367 A GB 2210367A
- Authority
- GB
- United Kingdom
- Prior art keywords
- formula
- aminofluorane
- halogen
- hydrogen
- process according
- 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.)
- Granted
Links
- MDQRDWAGHRLBPA-UHFFFAOYSA-N fluoroamine Chemical class FN MDQRDWAGHRLBPA-UHFFFAOYSA-N 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 5
- -1 nitro, amino Chemical group 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000003282 alkyl amino group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- OVHDZBAFUMEXCX-UHFFFAOYSA-N benzyl 4-methylbenzenesulfonate Chemical group C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=CC=C1 OVHDZBAFUMEXCX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 5
- MSIGTXLXMVOOQD-UHFFFAOYSA-N 2-phenoxyethyl 4-methylbenzenesulfonate Chemical group C1=CC(C)=CC=C1S(=O)(=O)OCCOC1=CC=CC=C1 MSIGTXLXMVOOQD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 150000005840 aryl radicals Chemical class 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 claims description 3
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 2
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 35
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- ZBCKLHSPIVVGMC-UHFFFAOYSA-N n-benzyl-n-fluoro-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(F)CC1=CC=CC=C1 ZBCKLHSPIVVGMC-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QECNBMJRDWINKS-UHFFFAOYSA-N n-fluoro-1-phenylmethanamine Chemical compound FNCC1=CC=CC=C1 QECNBMJRDWINKS-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- XDJUZAXDKYNVIJ-UHFFFAOYSA-N (2,4-dimethylphenyl)methyl 4-methylbenzenesulfonate Chemical compound C1(=CC=C(C=C1)S(=O)(=O)OCC1=C(C=C(C=C1)C)C)C XDJUZAXDKYNVIJ-UHFFFAOYSA-N 0.000 description 1
- MQHPFUBEBZPSOK-UHFFFAOYSA-N (2,5-dichlorophenyl)methyl 4-methylbenzenesulfonate Chemical compound CC1=CC=C(C=C1)S(=O)(=O)OCC1=C(Cl)C=CC(Cl)=C1 MQHPFUBEBZPSOK-UHFFFAOYSA-N 0.000 description 1
- JCQVMDZXBGBMOG-UHFFFAOYSA-N (2,5-dimethylphenyl)methyl 4-methylbenzenesulfonate Chemical compound C1(=CC=C(C=C1)S(=O)(=O)OCC1=C(C=CC(=C1)C)C)C JCQVMDZXBGBMOG-UHFFFAOYSA-N 0.000 description 1
- CFNIWCJEUPNISN-UHFFFAOYSA-N (4-chlorophenyl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=C(Cl)C=C1 CFNIWCJEUPNISN-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- HZONRRHNQILCNO-UHFFFAOYSA-N 1-methyl-2h-pyridine Chemical compound CN1CC=CC=C1 HZONRRHNQILCNO-UHFFFAOYSA-N 0.000 description 1
- SPXOTSHWBDUUMT-UHFFFAOYSA-N 138-42-1 Chemical class OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-N 0.000 description 1
- IRXDRTXDRBNEJI-UHFFFAOYSA-N 2-phenoxyethyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OCCOC1=CC=CC=C1 IRXDRTXDRBNEJI-UHFFFAOYSA-N 0.000 description 1
- LVAVWJHMTPWHSU-UHFFFAOYSA-N 2-phenylethyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OCCC1=CC=CC=C1 LVAVWJHMTPWHSU-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- FRCMMDZSDWDYGX-UHFFFAOYSA-N benzyl 4-bromobenzenesulfonate Chemical compound C1=CC(Br)=CC=C1S(=O)(=O)OCC1=CC=CC=C1 FRCMMDZSDWDYGX-UHFFFAOYSA-N 0.000 description 1
- DAZXBAMNNWGCMH-UHFFFAOYSA-N benzyl 4-nitrobenzenesulfonate Chemical compound C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)OCC1=CC=CC=C1 DAZXBAMNNWGCMH-UHFFFAOYSA-N 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001589 carboacyl group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
22 0367 1-16707/+ Process for the preparation of N-aralkylated
aminofluoranes The present invention relates to a process for the preparation of N- aralkylated aminofluoranes.
The aralkyl group is usually introduced by reacting the amino compound with an aralkyl halide, for example benzyl chloride or benzyl bromide, the reaction being carried out in polar media as well as in non-polar solvents and in the presence of alkali compounds. These methods, however, have the drawback that the final product is sometimes obtained in insufficient yield when using polycyclic amino compounds.
It is the object of the present invention to provide an improved process which permits an increase in yield and simultaneously affords products for technical use in excellent purity without complicated purification steps.
Specifically, the invention relates to a process for the preparation of Naralkylated aminofluoranes, which comprises reacting a 2-aminofluorane of formula xl 0 /R2 6 ---NH2 13 0 wherein the ring A is unsubstituted or substituted by halogen, nitro, amino, lower alkylamino or di-lower alkylamino, R1 and R3 are each independently of the other hydrogen, halogen, lower alkyl or lower alkoxy, R2 is hydrogen, lower alkyl or lower alkoxy, Xl and X2 are each independently of the other hydrogen, alkyl containing not more than 12 carbon atoms which is unsubstituted or substituted by halogen, hydroxy, cyano or lower alkoxy; or are cycloalkyl, tetrahydrofuryl, aryl or acyl, or -NX1X2 is a 5- or 6-membered, preferably saturated, heterocyclic radical, with an aralkylarylsulfonate of formula (2) Z-S02 -O-Y, wherein Z is an aryl radical and Y is an arylalkyl or aryloxyalkyl radical.
Halogen is, for example, fluorine, bromine, iodine or, preferably, chlorine.
In the definition of the radicals of the fluoranes, lower alkyl and lower alkoxy normally denote those groups or moieties which contain 1 to 5, preferably 1 to 3, carbon atoms. Lower alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butvl, see-butyl, tert-butyl or amvl, while lower alkoxy groups are, for example, methoxy, ethoxy, isopropoxy, tert-butoxy or tert-amyloxy.
Acyl is preferably formyl, lower alkanoyl such as acetyl or propionyl, or benzoyl. Further acyl radicals can be lower alkylsulfonyl, for example methyIsulfonyl or ethylsulfonyl as well as phenylsulfonyl. Cycloalkyl is, for example, cyclopentyl and, preferably, cyclohexyl.
In the meaning of Xl or X2 aryl is preferably phenyl or tolyl.
A heterocyclic radical -NX1X2 is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino or piperazino, for example methylpiperazino. Preferred saturated heterocyclic radicals -NXIX2 are pyrrolidino, piperidino or morpholino.
Xl and X2, each independently of the other, are preferably C,-C8-alkyl, cyclohexyl, phenyl or tolyl or most preferably lower alkyl or as -NX1X2 pyrrolidino The ring A is preferably not further substituted. If it does contain substituents, then these are preferably halogen or di-lower alkylamino.
Particularly good results are obtained by the process of the invention by using a fluorane of the indicated formula in which R2 is hydrogen or, preferably, lower alkyl or, most preferably, methyl.
Suitable aralkylarylsulfonates of formula (2) are those in which the aryl radical Z as well as the arylalkyl or aryloxyalkyl radical Y are unsubstituted or ring-substituted. Preferred substituents are halogens, nitro, trifluoromethyl, lower alkyl, preferably methyl, or lower alkoxy such as methoxy.
Particularly suitable sulfonates are those of formula (2), wherein Y is arylalkyl, for example benzenesulfonates, p-toluenesulfonates, pbromobenzenesulfonates or p-nitrobenzenesulfonates.
Examples of suitable sulfonates for introducing the aralkyl group are: benzyl p-toluenesulfonate, phenethyl benzenesulfonate, phenethyl ptoluenesulfonate, phenpropyl p-toluenesulfonate, a-methylbenzyl ptoluenesulfonate, phenpropyl benzenesulfonate, phenisopropyl ptoluenesulfonate, 4-chlorbenzyl p-toluenesulfonate, 4-methylbenzyl ptoluenesulfonate, 2,5-dimethylbenzyl p-toluenesulfonate, 2,5dichlorbenzyl p-toluenesulfonate, benzyl p-nitrobenzenesulfonate, benzyl p-bromobenzenesulfonate, 2,4-dimethylbenzyl p-toluenesulfonate, 4trifluoromethylbenzyl p-toluenesulfonate, 4-methoxybenzyl ptoluenesulfonate, 2-phenoxyethyl p-toluenesulfonate, 2-phenoxyethyl benzenesulfonate.
4 The preferred alkylsulfonate is benzyl p-toluenesulfonate. 2-Phenoxvethyl p-toluenesulfonate is also preferred.
The aminofluorane and the sulfonate are generally used in approximately stoichiometric proportions such that one aralkyl group, or preferably two aralkyl groups, are introduced per amino group. An excess of, for example, 10-15 % of one of the components is, however, also possible.
The reaction is conveniently carried out at elevated temperature preferably in the range from 80' to 12CC and in the presence of an acid acceptor.
Examples of suitable acid acceptors are alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal bicarbonates, alkali metal carbonates or tertiary nitrogen bases such as pyridine, N-methylpyridine or trialkylamines or also mixtures of these compounds. The preferred acid acceptor is sodium carbonate.
The reaction is preferably conducted in a non-polar, preferably aromatic, solvent, for example, benzene, toluene, xylene, a chlorobenzene such as dichlorobenzene or trichlorobenzene, or nitrobenzene. The preferred solvent is toluene or xylene.
After the condensation reaction the N-aralkylated aminofluorane is isolated in conventional manner, for example removing the solvent by steam distillation, collecting the product by filtration and drying it. If necessary, the aralkylated aminofluorane can be purified by recrystallisation, for example from isopropanol.
In the following Examples, percentages are by weight.
Example 1:.12 g of 2-amino-3-methyl-6-diethylaminofluorane (prepared in accordance with DE-B-2 001 864, Example 6) and 8.7 g of sodium carbonate are stirred in 28 g of toluene and the mixture is heated to 1OCC. Then a solution of 23.6 g of benzyl p-toluenesulfonate (prepared in accordance with Monatshefte-Chemie 82, pp. 452-459, 1951) in toluene is added dropwise at 100'-1050C over 2 hours. The reaction mixture is stirred for 8 hours at 1OCC and then poured into 100 g of water. The toluene phase is separated and washed three times with 50 g of water, dried over sodium sulfate and filtered. The toluene is distilled off under reduced pressure. The crude product is taken up in a small amount bf isopropyl alcohol, isolated in the form of a crystalline product at WC and dried, affording 12 g of a fluorane of formula 0 \ /. \\./ CH3 (CzHs)2N-1 11 1.1 1 Yield: 69 % of theory Melting point: 154-155C.
This compound immediately develops a red colour on acid-modified silica gel.
Example 2: 12 g of 2-amino-3-methyl-6-diethylaminofluorane and 12.4 g of potassium carbonate are heated to 1OCC in 60 ml of toluene. Then a solution of 39.3 g of benzyl p-toluenesulfonate in 51 g of toluene is added at 100-105C over 1 hour. Analysis by liquid chromatography of a sample taken from the reaction mixture shows already the presenc e of 68. 8 % of the condensate of formula (11). The reaction is kept for 1 hour at reflux temperature. Analysis of a fresh sample shows 99.2 % of reaction product.
The reaction product is filtered to remove inorganic salts, the filtrate is concentrated, and the residue is stirred in 75 ml of isopropanol. The crystallised condensate is isolated by filtration and dried, to give 10.5 g of product. Analysis by liquid chromatography shows that the filtrate contains a further 2.1 g of dibenzylaminofluorane of formula (11), but no corresponding monobenzylaminofluorane.
6 Comparison Example 12 g of 2-amino-3-methyl-6-diethylaminofluorane and 12.4 g of potassium carbonate are heated to 1OCC in 60 ml of toluene. Then a solution of 19 g of benzyl chloride in 51 g of toluene are added at 100-105'C over 1 hour. Analysis by liquid chromatography of a sample takeh from the reaction mixture shows that there is still no trace of the condensate of formula (11). The reaction mixture is kept for 1 hour at reflux temperature. Analysis of a fresh sample still shows no trace of dibenzylaminofluorane of formula (11), but only 3.2 % of the corresponding N-monobenzylated aminofluorane.
The reaction mixture is filtered to remove inorganic salts, the filtrate is concentrated, and the residue is stirred in 75 ml of isopropanol. 8.3 g of the starting 2-amino-3-methyl-6-diethylaminofluorane are recovered by isolating the crystallised product by filtration.
The condensa tion progresses slightly by concentrating the filtrate. Analysis by liquid chromatography shows a yield of 1.7 g of monobenzylaminofluorane and 1.1 g of dibenzylaminofluorane.
Example 3: 10 g of 2-amino-3-methyl-6-diethylaminofluorane, 10.4 g of potassium carbonate and 21.9 g of 2-phenoxyethyl p-toluenesulfonate (prepared in accordance with J. Org. Chem. 9 (1944), 235, 238-240) are stirred in 40 ml of xylene (mixture of isomers) for 11 hours at 137-140'C under reflux. A further 50 ml of xylene are added and the reaction mixture is extracted repeatedly with 100 ml of water at 5CC. The xylene phase is then concentrated until the condensate crystallises. The product is isolated by filtration, washed with isopropanol and dried, affording 3. 1 g of the compound of formula (C2Hs)zN-i 0 CH3 (12) //\NH-CH2CH2-0-'//.-.kk' in the form of colourless crystals which melt at 189-191'C. A solution of this compound in toluene develops an instant black colour on acid- modified silica gel.
Example 4: Column chromatography of the filtrate obtained according to Example 3 (silica gel; elution with a 20:1 mixture of toluenelethyl acetate) gives 2.8 g of the fluorane of formula (C2Hs)zN-1 H / 0 H 1 / CH3 (13) \V \N(CHzCH20-'/ \')2 11 -10 with a melting point of 117-119'C after recrystallisation from isopropanolltoluene (10:1).
This compound immediately develops a red colour on acid-modified silica gel.
Example 5: With efficient stirring, 9.6 g of 2-amino-6diethylaminofluorane, 6.9 g of potassium carbonate and 14.6 g of 2phenoxyethyl p-toluenesulfonate are heated in 50 ml of xylene and the mixture is kept under reflux for 22 hours at 133-137'C. To the reaction mixture are added 50 ml of xylene and, at 80% 100 ml of water. The xylene phase is then separated, washed repeatedly with water and concentrated, to give 20 g of crude reaction mixture. The fluorane compounds of formulae (14) and (15) are separated by column chromatography (silica gel; elution with a 10:1 mixture of toluene/ethyl acetate) and are each recrlystallised from isopropanol:
(C2H5)2N- _N(CH2CH2-0(14) m.p. 124-127'C.
8 0 (C2Hs) 2N- (15) m.p. 143-146'C.
The compound of formula (14) develops a green colour, and the compound of formula (15) a black colour, on acid-modified clay.
9
Claims (11)
1. A process for the preparation of a N-aralkylated aminofluorane, which comprises reacting a 2-aminofluorane of formula l Xl 0 R2 X>- 6 2-NH2 13 1 A 11 0 \\ /.-o wherein the ring A is unsubstituted or substituted by halogen, nitro, amino, lower alkylamino or di-lower alkylamino, R1 and R3 are each independently of the other hydrogen, halogen, lower alkyl or lower alkoxy, R2 is hydrogen, lower alkyl or lower alkoxy, X, and X2 are each independently of the other hvdrogen, alkyl containing not more than 12 carbon atoms which is unsubstituted or substituted by halogen, hydroxy, cyano or lower alkoxy; or are cycloalkyl, tetrahydrofuryl, aryl or acyl, or -NX1X2 is a 5- or 6-membered heterocyclic radical, with an aralkylarylsulfonate of formula (2) Z-S02 -O-Y, wherein Z is an aryl radical and Y is an arylalkyl or aryloxyalkyl radical.
2. A process according to claim 1, which comprises the use of an aralkylarylsulfonate of formula (2), wherein Y is the arylalkyl radical.
3. A process according to claim 1, wherein the aralkylarylsulfonate is an arylalkyl p-toluenesulfonate, an arylalkyl p-bromobenzenesulfonate or an arylalkyl p-nitrobenzenesulfanate.
- 10
4. A process according to claim 1, wherein the aralkylarylsulfonate is benzyl p-toluenesulfonate.
5. A process according to claim 1, wherein the aralkylarylsulfonate is 2phenoxyethyl p-toluenesulfonate.
6. A process according to claim 1, which comprises the use of a fluorane compound of formula (1), wherein R2 is hydrogen or lower alkyl.
7. A process according to claim 1, which comprises the use of a fluorane compound of formula (1), wherein Ra is methyl.
8. An aminofluorane of the formula Xl 0 \ / \'/R2 6 ?2 2-1-NH-YI A3 1 A 1 wherein the ring A is unsubstituted or substituted by halogen, nitro, amino, lower alkylamino or di-lower alkylamino, R, and R3 are each independently of the ther hydrogen, halogen, lower alkyl or lower alkoxy, R2 is hydrogen, lower alkyl or lower alkoxy, X, and X2 are each independently of the other hydrogen, alkyl containing not more than 12 carbon atoms which is unsubstituted or substituted by halogen, hydroxy, cyano or lower alkoxy; or are cycloalkyl, tetrahydrofuryl, aryl or acyl, or -NXIX2 is a 5- or 6-membered heterocyclic radical, and Y1 represents an aryloxyalkyl radical.
9. The aminofluorane of claim 8, wherein Y1 is 2-phenyloxyethyl.
10. The aminofluorane of claim 8, wherein R2 is methyl.
11. The aminofluorane of claim 8, wherein Xl and X2 are lower alkyl or NXIX2 is pyrrolidino, piperidino or morpholino.
FO 7.11PElsm Published 1988 at The Patent Office. State House. 6671 High Holborn. London WC1R 4TP. Further copies may be obtained from The Patent Office, Sales Branch, St Mai7 Cray. OrpL-gton. Kent 73RS 3RD Printed by Multiplex techmques ltd, St MaiT Cray, Kent. Con. 1'87
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH379887A CH672123A5 (en) | 1987-09-30 | 1987-09-30 | N-aryl:alkyl:amino:fluoran(s) prepn. |
| CH254588A CH675247A5 (en) | 1988-07-05 | 1988-07-05 | N-aryl:alkyl:amino:fluoran(s) prepn. |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8822146D0 GB8822146D0 (en) | 1988-10-26 |
| GB2210367A true GB2210367A (en) | 1989-06-07 |
| GB2210367B GB2210367B (en) | 1991-06-12 |
Family
ID=25690727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8822146A Expired - Lifetime GB2210367B (en) | 1987-09-30 | 1988-09-21 | Process for the perparation of n-aralkylated and/or n-aryloxy-alkylated aminofluoranes |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH01113393A (en) |
| DE (1) | DE3832756A1 (en) |
| GB (1) | GB2210367B (en) |
-
1988
- 1988-09-21 GB GB8822146A patent/GB2210367B/en not_active Expired - Lifetime
- 1988-09-27 DE DE19883832756 patent/DE3832756A1/en not_active Withdrawn
- 1988-09-30 JP JP63244693A patent/JPH01113393A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| CA 94(12):93 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01113393A (en) | 1989-05-02 |
| GB2210367B (en) | 1991-06-12 |
| GB8822146D0 (en) | 1988-10-26 |
| DE3832756A1 (en) | 1989-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7279264B2 (en) | Dyes and use thereof in thermal imaging members and methods | |
| US4330473A (en) | Recording material | |
| US5166350A (en) | Process for the manufacture of fluoran compounds | |
| US4016174A (en) | Benzoindole phthalides | |
| US5182389A (en) | Process for the preparation of 2-(2',4'-dihydroxyphenyl)-4,6-diaryl-s-triazines | |
| US4978768A (en) | Process for the preparation of alkyl esters of tetrachloro-2-cyano-benzoic acid | |
| US4806657A (en) | Process for the preparation of fluoran compounds which are substituted by basic groups | |
| US3113137A (en) | Method for isomerizing stereoisomeric xanthene and thioxanthene compounds via the use of oxalic acid | |
| GB2210367A (en) | Preparation of N-aralkylated and N-aryloxyalkylated aminofluoranes | |
| FR2731217A1 (en) | NOVEL TRICYCLIC DERIVATIVES, THEIR PREPARATION, THEIR APPLICATION TO THE PREPARATION OF OPTICALLY ACTIVE OR RACEMIC COLCHICINE AND THIOCOLCHICINE AND ANALOGS OR DERIVATIVES AND INTERMEDIATES | |
| US4673761A (en) | Process for preparing anti-inflammatory cycloalkylidenemethylphenylacetic acid derivatives | |
| US6084094A (en) | Oxidative process for preparing narwedine derivatives | |
| CN109232507A (en) | A kind of chromene compounds and preparation method thereof | |
| US2726264A (en) | Alpha-halogenosulfamylacetophenones | |
| US4083866A (en) | Sulfonylamidino aminobenzaldehyde compounds | |
| US4377703A (en) | Process for preparing benzoxanthene and benzothioxanthene dyestuffs | |
| US4381266A (en) | (N-Substituted benzoyl)halobenzoic acid anhydrides | |
| JPS6118943B2 (en) | ||
| SE437826B (en) | AZETIDINON DERIVATIVES FOR USE FOR THE PREPARATION OF OXADETIACEPHALOSPORIN ANTIBIOTICS | |
| JP2641002B2 (en) | Diphenyl sulfone compound | |
| GB2055368A (en) | E-homoeburnane derivatives | |
| KR100248370B1 (en) | Preparation of intermediate of (-)-3(s)-methylpyrido benzoxizine derivative | |
| US3998846A (en) | Process for preparing dibenzylamino fluoran compounds | |
| BE897007A (en) | PROCESS FOR THE PREPARATION OF 4-AZAPHTALIDE COMPOUNDS, THE COMPOUNDS OBTAINED THEREFROM AND THEIR USE AS CHROMOGENES IN A RECORDING MATERIAL | |
| US5268491A (en) | Process for the dehalogenation of naphthalene derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940921 |