GB598453A - Improvements relating to the manufacture of amidines - Google Patents
Improvements relating to the manufacture of amidinesInfo
- Publication number
- GB598453A GB598453A GB2274845A GB2274845A GB598453A GB 598453 A GB598453 A GB 598453A GB 2274845 A GB2274845 A GB 2274845A GB 2274845 A GB2274845 A GB 2274845A GB 598453 A GB598453 A GB 598453A
- Authority
- GB
- United Kingdom
- Prior art keywords
- heated
- chloride
- anhydrous
- product
- picrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001409 amidines Chemical class 0.000 title abstract 6
- 238000004519 manufacturing process Methods 0.000 title 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 24
- JFDZBHWFFUWGJE-UHFFFAOYSA-N Benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 abstract 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 5
- 239000011592 zinc chloride Substances 0.000 abstract 5
- 235000005074 zinc chloride Nutrition 0.000 abstract 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract 4
- 239000004202 carbamide Substances 0.000 abstract 4
- 125000005842 heteroatoms Chemical group 0.000 abstract 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 4
- FARXIDYHJAANGP-UHFFFAOYSA-N 4-methylsulfonylbenzonitrile Chemical compound CS(=O)(=O)C1=CC=C(C#N)C=C1 FARXIDYHJAANGP-UHFFFAOYSA-N 0.000 abstract 3
- 239000012458 free base Substances 0.000 abstract 3
- NKJIFDNZPGLLSH-UHFFFAOYSA-N 4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C=C1 NKJIFDNZPGLLSH-UHFFFAOYSA-N 0.000 abstract 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N Benzyl cyanide Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 abstract 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N Cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 abstract 2
- RBTARNINKXHZNM-UHFFFAOYSA-K Iron(III) chloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J Tin(IV) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract 2
- 125000002723 alicyclic group Chemical group 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 239000004411 aluminium Substances 0.000 abstract 2
- 229910052782 aluminium Inorganic materials 0.000 abstract 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 2
- 150000001412 amines Chemical class 0.000 abstract 2
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 2
- 125000003118 aryl group Chemical group 0.000 abstract 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 2
- 229940075930 picrate Drugs 0.000 abstract 2
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 abstract 2
- 125000001424 substituent group Chemical group 0.000 abstract 2
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-Nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 abstract 1
- QARLTYSAFQGMMB-UHFFFAOYSA-N 2-ethylbutanenitrile Chemical compound CCC(CC)C#N QARLTYSAFQGMMB-UHFFFAOYSA-N 0.000 abstract 1
- LIFFHRYRGZVVML-UHFFFAOYSA-N 2-nitrobenzenecarboximidamide;2,4,6-trinitrophenol Chemical compound NC(=N)C1=CC=CC=C1[N+]([O-])=O.OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O LIFFHRYRGZVVML-UHFFFAOYSA-N 0.000 abstract 1
- SWBDKCMOLSUXRH-UHFFFAOYSA-N 2-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=CC=C1C#N SWBDKCMOLSUXRH-UHFFFAOYSA-N 0.000 abstract 1
- RNYJYWQMEZWWPT-UHFFFAOYSA-N 4-Nitrobenzamidine Chemical compound NC(=N)C1=CC=C([N+]([O-])=O)C=C1 RNYJYWQMEZWWPT-UHFFFAOYSA-N 0.000 abstract 1
- XDJAAZYHCCRJOK-UHFFFAOYSA-N 4-methoxybenzonitrile Chemical compound COC1=CC=C(C#N)C=C1 XDJAAZYHCCRJOK-UHFFFAOYSA-N 0.000 abstract 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N Benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 abstract 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N Benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 abstract 1
- TWZHKUJTFMFCAD-UHFFFAOYSA-N C1([N+](=O)[O-])=CC([N+](=O)[O-])=CC([N+](=O)[O-])=C1O.C(C1=CC=CC=C1)(=N)N Chemical compound C1([N+](=O)[O-])=CC([N+](=O)[O-])=CC([N+](=O)[O-])=C1O.C(C1=CC=CC=C1)(=N)N TWZHKUJTFMFCAD-UHFFFAOYSA-N 0.000 abstract 1
- TVYYXOJXVFUONC-UHFFFAOYSA-N C1([N+](=O)[O-])=CC([N+](=O)[O-])=CC([N+](=O)[O-])=C1O.C1(=CC=CC=C1)CC(=N)N Chemical compound C1([N+](=O)[O-])=CC([N+](=O)[O-])=CC([N+](=O)[O-])=C1O.C1(=CC=CC=C1)CC(=N)N TVYYXOJXVFUONC-UHFFFAOYSA-N 0.000 abstract 1
- NJAKMTBVLRUCJE-UHFFFAOYSA-N C1([N+](=O)[O-])=CC([N+](=O)[O-])=CC([N+](=O)[O-])=C1O.C1(=CC=CC=C1)NC(C)=N Chemical compound C1([N+](=O)[O-])=CC([N+](=O)[O-])=CC([N+](=O)[O-])=C1O.C1(=CC=CC=C1)NC(C)=N NJAKMTBVLRUCJE-UHFFFAOYSA-N 0.000 abstract 1
- HSVDHGHAZAMKNW-UHFFFAOYSA-N C1([N+](=O)[O-])=CC([N+](=O)[O-])=CC([N+](=O)[O-])=C1O.[N+](=O)([O-])C1=C(C=CC=C1)NC(C1=CC=CC=C1)=N Chemical compound C1([N+](=O)[O-])=CC([N+](=O)[O-])=CC([N+](=O)[O-])=C1O.[N+](=O)([O-])C1=C(C=CC=C1)NC(C1=CC=CC=C1)=N HSVDHGHAZAMKNW-UHFFFAOYSA-N 0.000 abstract 1
- LQHZISZOQSEDIR-UHFFFAOYSA-N C1([N+](=O)[O-])=CC([N+](=O)[O-])=CC([N+](=O)[O-])=C1O.[N+](=O)([O-])C1=CC=C(C(=N)N)C=C1 Chemical compound C1([N+](=O)[O-])=CC([N+](=O)[O-])=CC([N+](=O)[O-])=C1O.[N+](=O)([O-])C1=CC=C(C(=N)N)C=C1 LQHZISZOQSEDIR-UHFFFAOYSA-N 0.000 abstract 1
- XBKBHBXBFORNDY-UHFFFAOYSA-N Cl.C1(CCCCC1)NC(C1=CC=C(C=C1)OC)=N Chemical compound Cl.C1(CCCCC1)NC(C1=CC=C(C=C1)OC)=N XBKBHBXBFORNDY-UHFFFAOYSA-N 0.000 abstract 1
- VARBBQAIMBHWDW-UHFFFAOYSA-N Cl.C1(CCCCC1)NC(CC1=CC=CC=C1)=N Chemical compound Cl.C1(CCCCC1)NC(CC1=CC=CC=C1)=N VARBBQAIMBHWDW-UHFFFAOYSA-N 0.000 abstract 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N Diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 abstract 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N Diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 abstract 1
- MPYOKHFSBKUKPQ-UHFFFAOYSA-N N'-phenylbenzenecarboximidamide Chemical compound C=1C=CC=CC=1C(N)=NC1=CC=CC=C1 MPYOKHFSBKUKPQ-UHFFFAOYSA-N 0.000 abstract 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-Methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 abstract 1
- BKJFKLRVGOPJDG-UHFFFAOYSA-N N-methyl-N-phenylbenzenecarboximidamide Chemical compound C=1C=CC=CC=1N(C)C(=N)C1=CC=CC=C1 BKJFKLRVGOPJDG-UHFFFAOYSA-N 0.000 abstract 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N Picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 abstract 1
- XCHIQWJYXUSYIL-UHFFFAOYSA-N [amino(phenyl)methylidene]-benzylazanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(N)=NCC1=CC=CC=C1 XCHIQWJYXUSYIL-UHFFFAOYSA-N 0.000 abstract 1
- 230000001476 alcoholic Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 229940114148 picric acid Drugs 0.000 abstract 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 abstract 1
- -1 polymethylene Polymers 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- ZVUUCUFDAHKLKT-UHFFFAOYSA-M sodium;2,4,6-trinitrophenolate Chemical compound [Na+].[O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O ZVUUCUFDAHKLKT-UHFFFAOYSA-M 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 229950002929 trinitrophenol Drugs 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Compounds containing the amidine grouping are manufactured by the interaction of a nitrile of the general formula R.CN (wherein R represents an alkyl, aryl, aralkyl or alicyclic group or a heterocyclic group having nitrogen as the hetero atom or atoms, which groups may contain substituents) with ammonia, urea or a monoamine of the general formula NHR1R2 (wherein R1 and R2 each represent an alkyl, aryl, aralkyl or alicyclic group or a heterocyclic group having nitrogen as the hetero atom or atoms, which groups may contain substituents, or R1 also hydrogen, or R1 and R2 jointly a divalent polymethylene chain) in the presence of aluminium chloride, zinc chloride, ferric chloride or stannic chloride. Alternatively, a preformed double compound of the metal salt and ammonia or the amine is used instead of the substances themselves. In examples: (1) benzyl cyanide is heated with urea and anhydrous zinc chloride, and the product is treated with sodium hydroxide solution, extracted with chloroform and the extract mixed with an alcoholic solution of picric acid to produce phenylacetamidine picrate; (2) benzonitrile is heated with anhydrous aluminium chloride while passing in dry ammonia, and the product is worked p up as in (1) to give benzamidine picrate; (3) p-nitrobenzonitrile is heated with aluminium hexamminochloride, and p-nitrobenzamidine is precipitated with sodium hydroxide solution, dissolved in dilute hydrochloric acid and treated with a solution of sodium picrate to precipitate the picrate of the amidine; (4) the aluminium hexamminochloride in (3) is replaced by anhydrous zinc chloride and dry ammonia; (5) p-nitrobenzonitrile is heated with urea and anhydrous aluminium or zinc chloride or stannic chloride, and the product is converted into p-nitrobenzamidine picrate via the free amidine; (6) anhydrous ferric chloride is used as the catalyst in (5); (7) o-nitrobenzonitrile is heated with urea and anhydrous aluminium chloride, and the product is converted to o-nitrobenzamidine picrate via the free amidine and the hydrochloride; (8) b -naphthonitrile similarly yields b -naphthamidine; (9) diethylacetonitrile is heated with cyclohexylamine and anhydrous aluminium chloride to produce N-cyclohexyl-a : a -diethylacetamidine hydrochloride; (10) to (15) benzyl cyanide similarly yields N-cyclohexyl phenylacetamidine hydrochloride, from which the free amidine may be liberated with sodium hydroxide solution; (16) anisonitrile similarly yields N-cyclohexylanisamidine hydrochloride; (17) p-methylsulphonylbenzonitrile sl heated with diethylamine and anhydrous aluminium chloride and the product is worked up as in (1) to give p-methylsulphonyl-N : N-diethylbenzamidine picrate; (18) benzonitrile and piperidine are similarly reacted and the reaction mixture is treated with sodium hydroxide solution to liberate N : N-pentamethylenebenzamidine; (19) p - methylsulphonylbenzonitrile similarly yields p-methyl sulphonyl - N : N - pentamethylenebenzamidine; (20) benzonitrile and benzylamine are heated with anhydrous aluminium chloride, and N-benzylbenzamidine hydrochloride is isolated amine are heated with anhydrous aluminium chloride to produce N-benzylaminoamidine hydrochloride; (22) acetonitrile and aniline are heated with anhydrous aluminium chloride and the product is converted to N-phenylacetamidine picrate via the free base; (23) benzonitrile and aniline are heated with anhydrous zinc chloride, and the product is treated with sodium hydroxide solution to liberate N-phenylbenzamidine; (24) benzonitrile and o-nitraniline are heated with anhydrous aluminium chloride, and the product is converted to N-(o-nitrophenyl)-benzamidine picrate via the free base and the hydrochloride; (25) 2 : 4-dichlorobenzonitrile and aniline are heated with anhydrous aluminium chloride, and N-phenyl-2 : 4 - dichlorobenzamidine hydrochloride is isolated via the free base; (26) benzonitrile and methylaniline are heated with anhydrous aluminium chloride, and the product is treated with sodium hydroxide solution to liberated N-methyl-N-phenylbenzamidine; (27) a -cyanopyridine and diphenylamine similarly yield N : N-diphenylpicolinamidine; (28) p-methylsulphonylbenzonitrile and a - aminopyridine similarly yield p - methylsulphonyl - N - a - pyridylbenzamidine; (29) benzonitrile is similarly treated to produce N-a -pyridylbenzamidine; (30) p : p1-dicyanodiphenoxypropane and aniline are heated with anhydrous aluminium chloride, and the product is treated with sodium hydroxide solution, hydrochloric acid, sodium hydroxide solution again and then benzenesulphonic acid to obtain a : g -bis-(p-N-phenylamidino) - phenoxypropane benzenesulphonate.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB598453A true GB598453A (en) | 1948-02-18 |
Family
ID=1737163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB2274845A Expired GB598453A (en) | 1945-09-04 | Improvements relating to the manufacture of amidines |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB598453A (en) |
-
1945
- 1945-09-04 GB GB2274845A patent/GB598453A/en not_active Expired
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