US1897220A - Process for the continuous preparation of a di-substituted guanidine - Google Patents
Process for the continuous preparation of a di-substituted guanidine Download PDFInfo
- Publication number
- US1897220A US1897220A US275646A US27564628A US1897220A US 1897220 A US1897220 A US 1897220A US 275646 A US275646 A US 275646A US 27564628 A US27564628 A US 27564628A US 1897220 A US1897220 A US 1897220A
- Authority
- US
- United States
- Prior art keywords
- guanidine
- aniline
- diphenyl
- tank
- pipe
- 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 - Lifetime
Links
- -1 di-substituted guanidine Chemical class 0.000 title description 9
- 238000000034 method Methods 0.000 title description 7
- 238000002360 preparation method Methods 0.000 title description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 28
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 9
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 5
- IEDHGYYAGIASNQ-UHFFFAOYSA-N [amino(anilino)methylidene]-phenylazanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[NH+]=C(N)NC1=CC=CC=C1 IEDHGYYAGIASNQ-UHFFFAOYSA-N 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 5
- 238000010924 continuous production Methods 0.000 description 5
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 5
- 229960004198 guanidine Drugs 0.000 description 5
- 150000002357 guanidines Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 229960000789 guanidine hydrochloride Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000003142 primary aromatic amines Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 101100165798 Arabidopsis thaliana CYP86A1 gene Proteins 0.000 description 1
- 101001076613 Homo sapiens Immortalization up-regulated protein Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 102100025886 Immortalization up-regulated protein Human genes 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
Definitions
- the present invention relates to the manufacture of di-substituted guanidines, particularly the diaryl-guanidines, such as diphenylguanidine,the ditolyl-guanidines and the like,
- aniline or other aromatic amine is placed in tank 1, from which it is removed through pipe 2, by means of pump 3, and is flowed through pipe 1 into a storage tank 5. From the tank 5 the aniline is flowed through a line controlled by a valve 6 into a measuring drum 8.
- the drum 8 is placed upon an ordinary platform scale 7, wherebythe rate of flow of the aniline from the drum is readily ascertained by the loss in weight indicated.
- the aniline flows from the drum 8 through the pipe 9 downward into the tower 10.
- cya-nogen chloride gas from any suitable source containing approximately 1.7% moisture is admitted to the tower 1() through the pipe 14 and passed upward in the tower counter-current to the aniline or other primary aromatic amine, where the two reagents are heated preferably between approximately 90 and 115o C.
- the following reaction takes place if aniline is employed as the primary aromatic amine:
- the tower 10 is filled with beads l5, as shown, or with any other substance such as pumice and the like, non-re.- act-ive to the materials supplied to the tower, and offering an obstructing' or baffling means to the flow of liquid and gases therethrough.
- the tower 10 is surrounded by a heating ele- 1923. Serial No. 275,646.
- ment 35 for example a jacket, for the admission of a heating medium, for example steam, by means of valve 27.
- the steam is allowed to escape from the jacket by pipe 29.
- a line 11, positioned at the bottom ofthe tower 10, permits the diphenyl or other diaryl guanidine hydro-chloride formed by the reaction ofthe amine and cyanogen chloride, to be dropped into tank 12.
- This tank is equipped with stirring means 13, Where the said diphenyl-guanidine hydrochloride is dissolved in sufficient water, heated by steam from pipe 28, to form approximately a 15% solution thereof. rlhis solution is withdrawn by pump 17 and forced through pipe 18 into chamber 19 and thence into a washing tank 20.
- Benzol, gasoline or other suitable solvent is supplied to the reaction product run into the tank 20 as described, in order to remove any uncombined aniline or other amine which may be present.
- the contents of the tank 2O is allowed to settle, whereupon the insoluble material, comprising the hydrochloride of diphenyl-guanidine, is withdrawn from the tank 20 and flowed through the pipe 24 into tank 23, while the benzol or other solvent employed in the washing step is removed from the tank 2() by means of pipe 21.
- the tank 23 is previously charged with a solution of alkaline material, for example a 15% solution of caustic soda, into which the diphenyl-guanidine hydrochloride is run.
- the acid salt of the aryl substituted guanidine is thereby neutralized and the free base is obtained.
- the slurry is agitated by means of stirrer 22 and the suspension is then removed from tank 23 through the line 26 by means of pump 25, and is run to a filter press, filtered, washed, dried and ground.
- Tower 10 hereinbefore mentioned, is provided with exit pipe to allow the removal of unreacted cyanogen chloride, which is passed by means of pipe 30 to coil 31, cooled by salt and ice in container 32. From coil 31, the condensed cyanogen chloride flows by gravity to storage, for example a cylinder 33, cooled for example by packing in ice in container 34, or may be connected by a pipe to the line 141 leading to the tower 10.
- aryl substituted guanidines may be readily manm'actured in a continuous manner by employing in place of the aniline mentioned in the example, other aromatic primary amines, such as ortho-toluidine, the 1nand p-to-luidines, the xylidenes and the like.
- aromatic primary amines such as ortho-toluidine, the 1nand p-to-luidines, the xylidenes and the like.
- steps in combination comprising continuously passing vapors of cyanogen chloride containing not more than 1.7% of water upward counter-current to a stream of aniline in a tower at a temperature p of approximately from 9() to 115o C., removing any unreacted aniline from ythe diphenyl guanidine hydrochloride thus produced by washing with benzene, and precipitating the diphenyl guanivdine by the addition of sodium hydroxide without the previous addition of a weaker alkali.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
W. P. TER HORST Feb. 14,v 1933.
Filed May '7, 1928 WN IT.
IMUP
wma
@WTO
[NI/ENTOR BY Wmuam D TEQ Hoas 4,70() A TTORNEY Patented Feb. 14, 1933 Unirse STATES PATENrosi-ice WILLIAM P. TER HORST, OF NITRO, WEST VIRGINIA, ASSIGNOR T THE RUBBER SERVICE LABORATORIES CO., OF AKRON, OHIO, A CORPORATION 0F OHIO PROCESS FOR THEY CONTINUOUS PREPARATION OF A DI-SUBSTITUTED GUANIDINE Application filed May 7,
The present invention relates to the manufacture of di-substituted guanidines, particularly the diaryl-guanidines, such as diphenylguanidine,the ditolyl-guanidines and the like,
by a substantially continuous process, whereby high yields of a pure product are realized.
The process will be readily understood from the following description with reference to the accompanying drawing which rep resents in sectional view a preferred arrangement of the apparatus necessary for practicing the invention.
Referring to the drawing, aniline or other aromatic amine is placed in tank 1, from which it is removed through pipe 2, by means of pump 3, and is flowed through pipe 1 into a storage tank 5. From the tank 5 the aniline is flowed through a line controlled by a valve 6 into a measuring drum 8.
rThe drum 8 is placed upon an ordinary platform scale 7, wherebythe rate of flow of the aniline from the drum is readily ascertained by the loss in weight indicated. The aniline flows from the drum 8 through the pipe 9 downward into the tower 10. At the same time, cya-nogen chloride gas from any suitable source containing approximately 1.7% moisture is admitted to the tower 1() through the pipe 14 and passed upward in the tower counter-current to the aniline or other primary aromatic amine, where the two reagents are heated preferably between approximately 90 and 115o C. The following reaction takes place if aniline is employed as the primary aromatic amine:
N H.CGH5
rllhe cyanogen chloride gas admitted by pipe 1lipasses through flow-meter 16, whereby the rate of flow of cyanogen chloride may be determined. The tower 10 is filled with beads l5, as shown, or with any other substance such as pumice and the like, non-re.- act-ive to the materials supplied to the tower, and offering an obstructing' or baffling means to the flow of liquid and gases therethrough.
The tower 10 is surrounded by a heating ele- 1923. Serial No. 275,646.
ment 35, for example a jacket, for the admission of a heating medium, for example steam, by means of valve 27. The steam is allowed to escape from the jacket by pipe 29. A line 11, positioned at the bottom ofthe tower 10, permits the diphenyl or other diaryl guanidine hydro-chloride formed by the reaction ofthe amine and cyanogen chloride, to be dropped into tank 12. This tank is equipped with stirring means 13, Where the said diphenyl-guanidine hydrochloride is dissolved in sufficient water, heated by steam from pipe 28, to form approximately a 15% solution thereof. rlhis solution is withdrawn by pump 17 and forced through pipe 18 into chamber 19 and thence into a washing tank 20. Benzol, gasoline or other suitable solvent is supplied to the reaction product run into the tank 20 as described, in order to remove any uncombined aniline or other amine which may be present. When the washing operation is completed, the contents of the tank 2O is allowed to settle, whereupon the insoluble material, comprising the hydrochloride of diphenyl-guanidine, is withdrawn from the tank 20 and flowed through the pipe 24 into tank 23, while the benzol or other solvent employed in the washing step is removed from the tank 2() by means of pipe 21. The tank 23 is previously charged with a solution of alkaline material, for example a 15% solution of caustic soda, into which the diphenyl-guanidine hydrochloride is run. The acid salt of the aryl substituted guanidine is thereby neutralized and the free base is obtained. The slurry is agitated by means of stirrer 22 and the suspension is then removed from tank 23 through the line 26 by means of pump 25, and is run to a filter press, filtered, washed, dried and ground.
Other aryl substituted guanidines may be readily manm'actured in a continuous manner by employing in place of the aniline mentioned in the example, other aromatic primary amines, such as ortho-toluidine, the 1nand p-to-luidines, the xylidenes and the like. By operating in the manner as described,iit has been found that high yields of an aryl substituted guanidine may be readily obtained from an aromatic primary amine. Moreover, the productie of an exceptionally high degree of purity.
What is claimed is 1. In the process of manufacturing a di aryl substituted guanidine by a continuous process, the steps in combination comprising continuously flowing vapors of cyanogen chlo- V ridecontaining not more than 1.7% of water a temperature of approximately 90 to 115o C.,
removing any unreacted amine from the diaryl guanidine hydrochloride, thus produced by washing with a neutral organic solvent and precipitating the diaryl guanidine by the addition of an alkali of constant strength.
3. In the process-of manufacturing diphenyl-guanidine by a continuous process, the steps in combination comprising continuously passing'vapors of cyanogen chloride containing not more'than 1.7% of water countercurrent to a stream of aniline in a tower at a temperature of approximately from to 115o C., removing any unreacted aniline from the diphenyl gua-nidine hydrochloride thus produced by washing Vwith' a neutral organic solvent, and precipitating the diphenyl guanidine by the addition of an alkali of constant strength.
4. In the process of manufacturing diphenyl-guanidine by a continuous process, the steps in combination comprising continuously passing vapors of cyanogenchloride containing not more than 1.7% of water upward counter-current to a stream of aniline in a tower at a temperature of approximately from 90 to 115 C., removing any unreacted aniline from the diphenyl guanidine hydrochloride thus produced by washing with a neutral organic solvent, and precipitating the diphenyl guanidine by the addition of an alkali of constant strength.
5. In the process of manufacturing diphenyl-guanidine by a continuous process, the
steps in combination comprising continuously passing vapors of cyanogen chloride containing not more than 1.7% of water upward counter-current to a stream of aniline in a tower at a temperature p of approximately from 9() to 115o C., removing any unreacted aniline from ythe diphenyl guanidine hydrochloride thus produced by washing with benzene, and precipitating the diphenyl guanivdine by the addition of sodium hydroxide without the previous addition of a weaker alkali.
6. In the process of manufacturing a diaryl substituted guanidine by a continuous signature.
WILLIAM P. TER HORST.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US275646A US1897220A (en) | 1928-05-07 | 1928-05-07 | Process for the continuous preparation of a di-substituted guanidine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US275646A US1897220A (en) | 1928-05-07 | 1928-05-07 | Process for the continuous preparation of a di-substituted guanidine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1897220A true US1897220A (en) | 1933-02-14 |
Family
ID=23053257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US275646A Expired - Lifetime US1897220A (en) | 1928-05-07 | 1928-05-07 | Process for the continuous preparation of a di-substituted guanidine |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1897220A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0231482A1 (en) * | 1985-12-18 | 1987-08-12 | Bayer Ag | Process for the isolation of diarylguanidines |
| EP0239864A1 (en) * | 1986-03-29 | 1987-10-07 | Bayer Ag | Process for isolation of diarylguanidines |
-
1928
- 1928-05-07 US US275646A patent/US1897220A/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0231482A1 (en) * | 1985-12-18 | 1987-08-12 | Bayer Ag | Process for the isolation of diarylguanidines |
| US4739117A (en) * | 1985-12-18 | 1988-04-19 | Bayer Aktiengesellschaft | Process for the isolation of diaryl guanidines |
| EP0239864A1 (en) * | 1986-03-29 | 1987-10-07 | Bayer Ag | Process for isolation of diarylguanidines |
| US4783553A (en) * | 1986-03-29 | 1988-11-08 | Bayer Aktiengesellschaft | Process for isolating diarylguanidines |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4095685B2 (en) | Method for producing toluylene diisocyanate, specific mixture of toluylene diamine and water, and use of the mixture for producing toluylene diisocyanate | |
| TWI552982B (en) | Preparation process of isocyanate | |
| JP2002502838A (en) | Method for producing methylene dianiline and methylene bis (phenyl isocyanate) | |
| US1897220A (en) | Process for the continuous preparation of a di-substituted guanidine | |
| JP6523856B2 (en) | Method for producing pentamethylene diisocyanate and apparatus for producing pentamethylene diisocyanate | |
| FI89041B (en) | Method for production of allylamine and quaternary diallylammonium compounds | |
| FR2478652A1 (en) | OXIDABLE DIENIC RUBBING CONTAINING AN ALKYLIC ALKYLATED DIPHENYL-PARA-PHENYLENE DIAMINE AS ANTIOXIDANT ON THE CORE, AT THE MELTING POINT | |
| US2247894A (en) | Manufacture of mercaptothiazoles | |
| US3255252A (en) | Process of reducing nitro compounds to the corresponding amines | |
| US1402338A (en) | Apparatus for the production of halogenated hydrocarbons | |
| US1422494A (en) | Method of manufacturing diphenylamine | |
| US1884509A (en) | Production of cyanogen celoride and substituted guanidines | |
| US1921587A (en) | Method for the manufacture of secondary aromatic amines | |
| US1918370A (en) | Plant for manufacturing chlorination products of caoutchouc | |
| US1836486A (en) | Manufacture of aromatic derivatives of 1-2 diamino ethane | |
| US2823221A (en) | Production of aromatic monoisocyanates in the gaseous phase | |
| Chattaway et al. | L.—The auto-reduction of hydrazines | |
| US1844518A (en) | Production of homolgues of aniline | |
| US1308356A (en) | of wilmington | |
| US3290355A (en) | Preparation of diacetonitrile | |
| US2784225A (en) | Condensing esters and amines to form amides | |
| US1727093A (en) | Process for producing substituted guanidines | |
| US2875225A (en) | Production of isocyanates | |
| US1429714A (en) | Process of making substituted amines | |
| US1555451A (en) | Isopropyl aromatic amine |