CA1051920A - Inner ammonium salts of phosphinic acids - Google Patents
Inner ammonium salts of phosphinic acidsInfo
- Publication number
- CA1051920A CA1051920A CA234,011A CA234011A CA1051920A CA 1051920 A CA1051920 A CA 1051920A CA 234011 A CA234011 A CA 234011A CA 1051920 A CA1051920 A CA 1051920A
- Authority
- CA
- Canada
- Prior art keywords
- oxo
- oxaphospholane
- methyl
- amine
- alkyl
- 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
- 239000002253 acid Substances 0.000 title abstract description 3
- 150000007513 acids Chemical class 0.000 title abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- -1 2-oxo-2-ethyl-4-methyl-1,2-oxaphospholane Chemical compound 0.000 claims description 8
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- OSNNATVBPNXCAF-UHFFFAOYSA-N 2-methyl-1,2$l^{5}-oxaphospholane 2-oxide Chemical compound CP1(=O)CCCO1 OSNNATVBPNXCAF-UHFFFAOYSA-N 0.000 claims description 6
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 3
- LAGMXDJAEGBQMG-UHFFFAOYSA-N 2-ethyl-1,2$l^{5}-oxaphospholane 2-oxide Chemical compound CCP1(=O)CCCO1 LAGMXDJAEGBQMG-UHFFFAOYSA-N 0.000 claims description 2
- BDBZTOMUANOKRT-UHFFFAOYSA-N 4-[2-(4-aminocyclohexyl)propan-2-yl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1C(C)(C)C1CCC(N)CC1 BDBZTOMUANOKRT-UHFFFAOYSA-N 0.000 claims description 2
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- QKYWADPCTHTJHQ-UHFFFAOYSA-N n,2-dimethylpropan-1-amine Chemical compound CNCC(C)C QKYWADPCTHTJHQ-UHFFFAOYSA-N 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- PLDGWDUACROPGN-UHFFFAOYSA-N O=P1OCCC1C Chemical compound O=P1OCCC1C PLDGWDUACROPGN-UHFFFAOYSA-N 0.000 claims 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
INNER AMMONIUM SALTS OF PHOSPHINIC ACIDS
Abstract of the Disclosure:
Zwitterionic compounds of the formulae and
Abstract of the Disclosure:
Zwitterionic compounds of the formulae and
Description
~.05~
It is known to prepare cyclic phosphinic acid esters in dif-ferent ways. Suitable processes for example are described in US Patent Specifications Nos. 2,916,510, 2,953,591 and 2,648, 695. Little is known up to now about the reactivity of such com-pounds also named phostones or 2-oxo-2-alkyl-1.2-oxaphosphola-nes. US Patent Specifications Nos. 2,916,510 and 2,953,591 on-ly note that the cyclic phosphinic acid esters are chemically stable in a wide temperature range.
It has been manifested surprisingly that these compounds may be reacted in simple manner with primary or secondary, mo-novalent or bivalent, aliphatic or aromatic amines to yield zwitterionic salts of novel phosphinic acids presenting a se-ries of technically rather valuable properties.
The present invention consequently provides zw~itterionic compounds of the formulae O-P-CH-CH-CH - ~ R
O H
and IR Rl IR2 6~13 ~13 R2 Rl 0-~-CH-CH-CH2-N-R5-~-CH2-~H-CH-~-O H H o It has moreover been found that said zwitterionic compounds may be prepared advantageously by reacting 2-oxo-2-alkyl-1.2-oxaphospholane of the formula R2f ~' O R
29 with primary or secondary, monovalent or bivalent, aliphatic ; - 2 - ~
~ .
.
l~lg~O
or aromatic amines.
R, Rl, R2 and R3 signify hydrogen or simple aliphatic hy-drocarbon radicals such as methyl, ethyl and propyl.
R4 may signify an alkyl, a cycloalkyl or an aralkyl radi-cal such as methyl, cyclohexyl or aralkyl having up to 15 car-bon atoms or an olefinic radical having up to 12 carbon atoms such as an allyl radical.
R5 stands for a bivalent alkylene or aralkylene radical or a cycloalkylene radical such as for example -CH2-CH2-CH2 ~ H2C ~ CH2 ' H ~ 2 ~ H
having up to 25 carbon atoms.
The following equation illustrates the invention:
n ,3 \ ~ O + H2N- ~ O-P-CH2-CH2 2 2 The starting compounds generally are reacted in a stoich-iometric proportion and the reaction is performed at a tempera-tur~ of from 50 to 250, preferably of from 80 to 180C. It may be operated thereby with or without a solvent or a dispersing agent. Highly boiling ethers such as diglycol dimethyl ethers, 25 aromatic compounds such as xylene, chlorobenzene etc. may be used, for example. It is also possible to use one of the star-ting components, for example, the amine, in a greater excess, simultaneously acting as a solvent. In the case of stoichiome-29 tric conversions without using a solvent the salts most fre-~ . .
, . : .
.-:
~ 5~
quently are obtained in a quar~titative yield, generally in a cry-stallized form. When heating in the solvent the reaction product generally is obtained in the form of a colorless, crystalline precipitate which may increase by cooling after termination of the reaction and be easily isolated by simple filtration.
The smooth method of carrying out the reaction yielding co-lorless products of a high purity in the case of a number of mono- and diamines with a practically quantitative yield is surprising and unexpected.
As suitable phosphlanes for the reaction there may be men-tioned, for example, 2-oxo-methyl-1.2-oxaphospholane, 2-oxo-2-ethyl-1.2-oxaphospholane, 2-oxo-3-methyl-1.2-oxaphospholane,2-oxo-2-ethyl-4-methyl-1.2-oxaphospholane,2-oxo-2-hexyl-1.2-oxa-phospholane.
Suitable amino compounds, for example, are methylamine, di-methylamine, allylamine, octylamine, cyclohexylamine, methyl-isobutylamine, benzylamine, ethylene amine, diamino propane-1.3, bis-aminomethylcyclohexane, dimethyl-bis-(4-amino-cyclohexyl)-methane.
The novel compounds may be used as anti-static agents, pri-mers for metallic surf~ces, as long-acting desinfectant owing to their absolute resistance to hydrolysis and as flotation and emulsifying auxiliaries. They may moreover be used as interme-diates for the textile finishing and colouring.
The following examples illustrate the invention:
E X A M P L E l:
40 g of freshly distilled cyclohexylamine were added to lO g of 2-oxo-2-methyl-1.2-oxaphospholane in a round bottom 29 flask, heated till boiling and refluxed for 4 hours. The cry-105~
stall precipitation already starting ~uring the boiling prGce~s was completed by cooling. After filtering off with suction and washing with ice-cold methanol 11.0 g of colorless crystalls of a melting point of from 251 to 252C were obtained, of the formula:
CH3 ~9 calculatedfound o-P-CH2-CH2-CH2 NH2 C 11 6 C 54.8 54.8 ~
H 10.1 10.1 %
~ 6.4 6.6 %
By concentrating the mother liquor another analytically pure crystall fraction having the exact melting point was obtained from ethanol after recrystallisation in an amount of 6.5 g. The total yield of analytically pure material was 96 %.
E X A M P L E 2:
12 g of 2-oxo-2-methyl-1.2-oxaphospholane (0.1 mole) were carefully melt with 9.9 g of cyclohexylamine (0.1 mole) in a Schlenk tube under a nitrogen atmosphere and kept in a heating furnace for 2 days at a temperature of 80 to 90C. The fluid molten mass got viscous after some hours and colorless cry-stalls slowly precipitated therefrom. The mixture solidified within a period of some hours or days to give the analytically pure adduct. Crystallisation may be accelerated in the presen-ce of ethanol or isopropanol. A recrystallisation of the pro-ducts was not required generally.
- E X A M P L E 3: -15.2 g of bis-(4-amino-cyclohexyl)-methane(72.4 moles) were slowly melt in an oil bath with 17.4 g of 2-oxo-2-methyl-29 1-2-oxaphosph~lane (144.8 moles) in a Schlenk tube while inten-: _ 5 _ ' .~
.~
~s~9~o sively flushing with nitrogen and allowed to stand for 20 hours at 160C. The colorless, crystalline log could be easily crush-ed at room temperature and be drawn off.
~ o-p-cH2-cH2-NH2-c6Hlo-cH2-c6Hlo NH2 2 2 C H N
calculated 56,0 9,8 6,2 found 55,8 9,8 6,2 E X A M P L E 4:
3.7 g of diaminopropane -1.3 (50 mmoles) were slowly heat-ed to 130C with 12.0 g of 2-oxo-2-methyl-1.2-oxaphospholane (100 mmoles) in a Schlenk tube under a nitrogen atmosphere and allowed to stand for 3 hours. After heating for another 6 to 8 hours to 170C a colorless to weakly yellow mass was obtained completely crystallizing when cooling but still containing small amounts of easily volatile portions. By drying in a pistol at 100 C and under one torr the analytically pure product was obtained in a yield of 92 % of the following formula:
~3 1 3 ~ ~ CH3 O-P-cH2-cH2-NH2-(cH2)3 NH2 CH2 2 n o o C H N
calculated 42.0 9.0 8.9 found 41.9 9.2 8.9 E X A M P L E 5:
When heating the components of example 4 in diglycoldi-methyl ether to 160C a glassy product precipitated which could ' :' ~OS192V
be converted by means of ethanolic hydrochloric acid into the crystalline chlorhydric salt of the compound of example 4 of the formula:
~ CH3 ~ CH3 5HO-P-CH2-CH2-NH2-(CH3)3 NH2 C 2 2 I~
O Cl~ Cl~ O
having a melting point of 236 to 239C, in a yield of 45%, after splitting off the liquid phase and washing with ethanol.
C H N Cl calculated 34.1 7.8 7.2 18.2 found 33.9 7.2 7.2 18.2 The compound free from halogen could be recovered from the hydrochloric salt by means of alcoholic potassium hydroxi-de solution.
E X A M P L E 6:
11.6 g of hexamethylene diamine (0.1 mole) were melt with 24 g of 2-oxo-2-methyl-1.2-oxaphospholane (0.2 mole) in a Schlenk tube under a nitrogen atmosphere at 150C and allowed to stand for 20 hours at 180 C. A wax-like, partly crystal-line product was obtained when cooling, the analysis where-of corresponded to the reaction yeilding the double inner ammonium salt. ~ `
.~ .
It is known to prepare cyclic phosphinic acid esters in dif-ferent ways. Suitable processes for example are described in US Patent Specifications Nos. 2,916,510, 2,953,591 and 2,648, 695. Little is known up to now about the reactivity of such com-pounds also named phostones or 2-oxo-2-alkyl-1.2-oxaphosphola-nes. US Patent Specifications Nos. 2,916,510 and 2,953,591 on-ly note that the cyclic phosphinic acid esters are chemically stable in a wide temperature range.
It has been manifested surprisingly that these compounds may be reacted in simple manner with primary or secondary, mo-novalent or bivalent, aliphatic or aromatic amines to yield zwitterionic salts of novel phosphinic acids presenting a se-ries of technically rather valuable properties.
The present invention consequently provides zw~itterionic compounds of the formulae O-P-CH-CH-CH - ~ R
O H
and IR Rl IR2 6~13 ~13 R2 Rl 0-~-CH-CH-CH2-N-R5-~-CH2-~H-CH-~-O H H o It has moreover been found that said zwitterionic compounds may be prepared advantageously by reacting 2-oxo-2-alkyl-1.2-oxaphospholane of the formula R2f ~' O R
29 with primary or secondary, monovalent or bivalent, aliphatic ; - 2 - ~
~ .
.
l~lg~O
or aromatic amines.
R, Rl, R2 and R3 signify hydrogen or simple aliphatic hy-drocarbon radicals such as methyl, ethyl and propyl.
R4 may signify an alkyl, a cycloalkyl or an aralkyl radi-cal such as methyl, cyclohexyl or aralkyl having up to 15 car-bon atoms or an olefinic radical having up to 12 carbon atoms such as an allyl radical.
R5 stands for a bivalent alkylene or aralkylene radical or a cycloalkylene radical such as for example -CH2-CH2-CH2 ~ H2C ~ CH2 ' H ~ 2 ~ H
having up to 25 carbon atoms.
The following equation illustrates the invention:
n ,3 \ ~ O + H2N- ~ O-P-CH2-CH2 2 2 The starting compounds generally are reacted in a stoich-iometric proportion and the reaction is performed at a tempera-tur~ of from 50 to 250, preferably of from 80 to 180C. It may be operated thereby with or without a solvent or a dispersing agent. Highly boiling ethers such as diglycol dimethyl ethers, 25 aromatic compounds such as xylene, chlorobenzene etc. may be used, for example. It is also possible to use one of the star-ting components, for example, the amine, in a greater excess, simultaneously acting as a solvent. In the case of stoichiome-29 tric conversions without using a solvent the salts most fre-~ . .
, . : .
.-:
~ 5~
quently are obtained in a quar~titative yield, generally in a cry-stallized form. When heating in the solvent the reaction product generally is obtained in the form of a colorless, crystalline precipitate which may increase by cooling after termination of the reaction and be easily isolated by simple filtration.
The smooth method of carrying out the reaction yielding co-lorless products of a high purity in the case of a number of mono- and diamines with a practically quantitative yield is surprising and unexpected.
As suitable phosphlanes for the reaction there may be men-tioned, for example, 2-oxo-methyl-1.2-oxaphospholane, 2-oxo-2-ethyl-1.2-oxaphospholane, 2-oxo-3-methyl-1.2-oxaphospholane,2-oxo-2-ethyl-4-methyl-1.2-oxaphospholane,2-oxo-2-hexyl-1.2-oxa-phospholane.
Suitable amino compounds, for example, are methylamine, di-methylamine, allylamine, octylamine, cyclohexylamine, methyl-isobutylamine, benzylamine, ethylene amine, diamino propane-1.3, bis-aminomethylcyclohexane, dimethyl-bis-(4-amino-cyclohexyl)-methane.
The novel compounds may be used as anti-static agents, pri-mers for metallic surf~ces, as long-acting desinfectant owing to their absolute resistance to hydrolysis and as flotation and emulsifying auxiliaries. They may moreover be used as interme-diates for the textile finishing and colouring.
The following examples illustrate the invention:
E X A M P L E l:
40 g of freshly distilled cyclohexylamine were added to lO g of 2-oxo-2-methyl-1.2-oxaphospholane in a round bottom 29 flask, heated till boiling and refluxed for 4 hours. The cry-105~
stall precipitation already starting ~uring the boiling prGce~s was completed by cooling. After filtering off with suction and washing with ice-cold methanol 11.0 g of colorless crystalls of a melting point of from 251 to 252C were obtained, of the formula:
CH3 ~9 calculatedfound o-P-CH2-CH2-CH2 NH2 C 11 6 C 54.8 54.8 ~
H 10.1 10.1 %
~ 6.4 6.6 %
By concentrating the mother liquor another analytically pure crystall fraction having the exact melting point was obtained from ethanol after recrystallisation in an amount of 6.5 g. The total yield of analytically pure material was 96 %.
E X A M P L E 2:
12 g of 2-oxo-2-methyl-1.2-oxaphospholane (0.1 mole) were carefully melt with 9.9 g of cyclohexylamine (0.1 mole) in a Schlenk tube under a nitrogen atmosphere and kept in a heating furnace for 2 days at a temperature of 80 to 90C. The fluid molten mass got viscous after some hours and colorless cry-stalls slowly precipitated therefrom. The mixture solidified within a period of some hours or days to give the analytically pure adduct. Crystallisation may be accelerated in the presen-ce of ethanol or isopropanol. A recrystallisation of the pro-ducts was not required generally.
- E X A M P L E 3: -15.2 g of bis-(4-amino-cyclohexyl)-methane(72.4 moles) were slowly melt in an oil bath with 17.4 g of 2-oxo-2-methyl-29 1-2-oxaphosph~lane (144.8 moles) in a Schlenk tube while inten-: _ 5 _ ' .~
.~
~s~9~o sively flushing with nitrogen and allowed to stand for 20 hours at 160C. The colorless, crystalline log could be easily crush-ed at room temperature and be drawn off.
~ o-p-cH2-cH2-NH2-c6Hlo-cH2-c6Hlo NH2 2 2 C H N
calculated 56,0 9,8 6,2 found 55,8 9,8 6,2 E X A M P L E 4:
3.7 g of diaminopropane -1.3 (50 mmoles) were slowly heat-ed to 130C with 12.0 g of 2-oxo-2-methyl-1.2-oxaphospholane (100 mmoles) in a Schlenk tube under a nitrogen atmosphere and allowed to stand for 3 hours. After heating for another 6 to 8 hours to 170C a colorless to weakly yellow mass was obtained completely crystallizing when cooling but still containing small amounts of easily volatile portions. By drying in a pistol at 100 C and under one torr the analytically pure product was obtained in a yield of 92 % of the following formula:
~3 1 3 ~ ~ CH3 O-P-cH2-cH2-NH2-(cH2)3 NH2 CH2 2 n o o C H N
calculated 42.0 9.0 8.9 found 41.9 9.2 8.9 E X A M P L E 5:
When heating the components of example 4 in diglycoldi-methyl ether to 160C a glassy product precipitated which could ' :' ~OS192V
be converted by means of ethanolic hydrochloric acid into the crystalline chlorhydric salt of the compound of example 4 of the formula:
~ CH3 ~ CH3 5HO-P-CH2-CH2-NH2-(CH3)3 NH2 C 2 2 I~
O Cl~ Cl~ O
having a melting point of 236 to 239C, in a yield of 45%, after splitting off the liquid phase and washing with ethanol.
C H N Cl calculated 34.1 7.8 7.2 18.2 found 33.9 7.2 7.2 18.2 The compound free from halogen could be recovered from the hydrochloric salt by means of alcoholic potassium hydroxi-de solution.
E X A M P L E 6:
11.6 g of hexamethylene diamine (0.1 mole) were melt with 24 g of 2-oxo-2-methyl-1.2-oxaphospholane (0.2 mole) in a Schlenk tube under a nitrogen atmosphere at 150C and allowed to stand for 20 hours at 180 C. A wax-like, partly crystal-line product was obtained when cooling, the analysis where-of corresponded to the reaction yeilding the double inner ammonium salt. ~ `
.~ .
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A zwitterionic compound of the formulae or wherein R, R1, R2 and R3 each represents hydrogen or simple aliphatic hydrocarbon radicals, R4 represents alkyl, cycloalkyl or aralkyl groups having up to 15 carbon atoms, or an olefinic radical having up to 12 carbon atoms, and R5 represents bivalent alkylene, cycloalkylene or aralkylene radicals having up to 25 carbon atoms.
2. A compound as claimed in claim 1 in which R, R1 and R2 are selected from the group of methyl, ethyl and propyl, R4 represents methyl, cyclohexyl or octyl and R5 represents -CH2-CH2-CH2-, or .
3. Process for the preparation of a compound of the formulae as set forth in claim 1 in which a 2-oxo-2-alkyl-1,2-oxaphospholane of the formula wherein R, R1, and R2 are as defined in claim 1 is reacted with a primary or secondary, monovalent or bivalent amine in the presence or absence of a solvent and at a temperature of from 50 to 250°C.
4. A process as claimed in claim 3 in which the 2-oxo-2-alkyl-1,2-oxaphospholane and the amine are present in stoichiometric proportions and the reaction is carried out at a temperature of from 80 to 180°C.
5. A process as claimed in claim 3 or claim 4 in which the reaction is carried out in the presence of a solvent.
6. A process as claimed in claim 3 or claim 4 in which the reaction is carried out in the absence of a solvent.
7. A process as claimed in claim 3 in which the amine is present in an excess amount and the excess amine acts as a solvent.
8. A process as claimed in claim 3 in which 2-oxo-2-alkyl-1,2-oxaphospholane is selected from the group of 2-oxo-methyl-1,2-oxaphospholane, 2-oxo-2-ethyl-1,2-oxaphospholane, 2-oxo-3-methyl-1,2-oxaphospholane, 2-oxo-2-ethyl-4-methyl-1,2-oxaphospholane, and 2-oxo-2-hexyl-1,2-oxaphospholane.
9. A process as claimed in claim 3 or claim 8 in which the amine is selected from the group of methylamine, dimethylamine, allylamine, octylamine, cyclohexylamine, methylisobutylamine, benzylamine, ethylene amine, diamino propane-1,3, bis-aminomethylcyclohexane and dimethyl-bis-(4-amino-cyclohexyl)-methane.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2440239A DE2440239A1 (en) | 1974-08-22 | 1974-08-22 | INNER AMMONIUM SALTS OF PHOSPHIC ACIDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1051920A true CA1051920A (en) | 1979-04-03 |
Family
ID=5923804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA234,011A Expired CA1051920A (en) | 1974-08-22 | 1975-08-21 | Inner ammonium salts of phosphinic acids |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5143726A (en) |
| AT (1) | AT332884B (en) |
| BE (1) | BE832681A (en) |
| CA (1) | CA1051920A (en) |
| DE (1) | DE2440239A1 (en) |
| FR (1) | FR2282431A1 (en) |
| GB (1) | GB1525262A (en) |
| IT (1) | IT1041954B (en) |
| NL (1) | NL7509753A (en) |
| ZA (1) | ZA755366B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127876A (en) * | 2011-11-22 | 2013-06-05 | 中国科学院大连化学物理研究所 | Quaternary amination organic phosphine surfactant and synthetic method thereof |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2723137C3 (en) * | 1977-05-23 | 1980-06-26 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of methyl [2- <2,4,6tribromophenylcarbamoyl-) ethyl] phosphinic acid |
| US5457095A (en) * | 1984-10-12 | 1995-10-10 | Ciba-Geigy Corporation | Substituted propane-phosponous acid compounds |
| US5243062A (en) * | 1984-10-12 | 1993-09-07 | Ciba-Geigy Corporation | Substituted propane-phosphonous acid compounds |
| US5300679A (en) * | 1987-12-04 | 1994-04-05 | Ciba-Geigy Corporation | Substituted propane-phosphinic acid compounds |
| GB8728483D0 (en) * | 1987-12-04 | 1988-01-13 | Ciba Geigy Ag | Chemical compounds |
| US5190933A (en) * | 1987-12-04 | 1993-03-02 | Ciba-Geigy Corporation | Substituted propane-phosphinic acid compounds |
| US5281747A (en) * | 1989-05-13 | 1994-01-25 | Ciba-Geigy Corporation | Substituted aminoalkylphosphinic acids |
| US5190934A (en) * | 1989-06-03 | 1993-03-02 | Ciba-Geigy Corporation | P-subsituted propane-phosphinic acid compounds |
| IL98502A (en) * | 1990-06-22 | 1998-04-05 | Ciba Geigy Ag | Aminoalkane phosphinic acid derivatives, process for their preparation and pharmaceutical compositions containing them |
| EP0543780A3 (en) * | 1991-11-21 | 1993-09-01 | Ciba-Geigy Ag | Novel aminoalkanephosphinic acids and their salts |
| AU662404B2 (en) * | 1992-05-08 | 1995-08-31 | Novartis Ag | Novel N-aralkyl- and N-heteroaralkyl-aminoalkanephosphinic acids |
-
1974
- 1974-08-22 DE DE2440239A patent/DE2440239A1/en not_active Withdrawn
-
1975
- 1975-08-15 NL NL7509753A patent/NL7509753A/en not_active Application Discontinuation
- 1975-08-20 JP JP50100238A patent/JPS5143726A/ja active Pending
- 1975-08-20 IT IT26470/75A patent/IT1041954B/en active
- 1975-08-21 CA CA234,011A patent/CA1051920A/en not_active Expired
- 1975-08-21 AT AT649675A patent/AT332884B/en not_active IP Right Cessation
- 1975-08-21 FR FR7525875A patent/FR2282431A1/en active Granted
- 1975-08-21 ZA ZA00755366A patent/ZA755366B/en unknown
- 1975-08-22 BE BE159411A patent/BE832681A/en unknown
- 1975-08-22 GB GB34977/75A patent/GB1525262A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127876A (en) * | 2011-11-22 | 2013-06-05 | 中国科学院大连化学物理研究所 | Quaternary amination organic phosphine surfactant and synthetic method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2440239A1 (en) | 1976-03-04 |
| FR2282431B1 (en) | 1978-12-08 |
| ATA649675A (en) | 1976-02-15 |
| BE832681A (en) | 1976-02-23 |
| FR2282431A1 (en) | 1976-03-19 |
| AT332884B (en) | 1976-10-25 |
| NL7509753A (en) | 1976-02-24 |
| IT1041954B (en) | 1980-01-10 |
| ZA755366B (en) | 1976-08-25 |
| GB1525262A (en) | 1978-09-20 |
| JPS5143726A (en) | 1976-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1051920A (en) | Inner ammonium salts of phosphinic acids | |
| US3243429A (en) | Aziridinyl siloxanes | |
| US4053505A (en) | Preparation of n-phosphonomethyl glycine | |
| US4927952A (en) | Silanol condensation products | |
| US2502478A (en) | Tetrafluorosuccinic acid derivatives and their preparation | |
| US4131609A (en) | Silicon-phthalocyanine-siloxy monomers | |
| US4517122A (en) | Cyclic peptides | |
| US3997604A (en) | Mixtures of perfluoroaliphatic substituted amino compounds and the method for preparing the same | |
| CS240964B2 (en) | Preparation method of n-phosphonomethylglycine | |
| US4885392A (en) | Derivatives of 1,3-bissubstituted 2-propanol containing amino groups, methods for their preparation and their use | |
| US2824884A (en) | Amides of perchlorofluorocarboxylic acids and process for the preparation thereof | |
| DK168213B1 (en) | Alkoxymethyl ether and alkoxymethyl ester derivatives of glycerol and process for the preparation of 9- (1,3-dihydroxy-2-propoxymethyl) guanine and ethers and esters thereof | |
| NO802356L (en) | FUNCTIONALLY SUBSTITUTED PHENOXYLKYL ALCOXYSILANES AND PROCEDURES FOR THEIR PREPARATION | |
| US3699165A (en) | N,n-bis{8 2-hydroxyalkyl{9 -2-hydroxyethoxyacetamide and process for making the same | |
| US4132842A (en) | Silicon-phthalocyanine-siloxane polymers | |
| US5081260A (en) | 3-(2-oxo-1-pyrrolidinyl)-propylsilanes and method for preparing the silane compounds | |
| US4625043A (en) | Ethylidenenorbornyl dimethylmethacryloxysilane | |
| US2991299A (en) | Titanium trialkanolamine derivatives | |
| US4495366A (en) | Process for making trifunctional primary amine crosslinker | |
| US4600535A (en) | Cyclic peptides | |
| Krawczyk | The Mannich Reaction of Diethyl Phosphonoacetic Acid. A Novel Route to 1-(N, N-Dialkylamino) Methylvinylphosphonates | |
| US3592833A (en) | Tris-(organosilylmethyl)-amines and production thereof | |
| HU194257B (en) | Process for preparing n-(phosphonomethyl)-glycine | |
| US3049559A (en) | Ureas | |
| Gajda et al. | A convergent one-pot synthesis of secondary amines via aza-Wittig reaction |