CA1117970A - Phosphorbetaines and process for making them - Google Patents
Phosphorbetaines and process for making themInfo
- Publication number
- CA1117970A CA1117970A CA000259646A CA259646A CA1117970A CA 1117970 A CA1117970 A CA 1117970A CA 000259646 A CA000259646 A CA 000259646A CA 259646 A CA259646 A CA 259646A CA 1117970 A CA1117970 A CA 1117970A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- reaction
- catalyst
- phosphobetaines
- phosphobetaine
- 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
- 238000000034 method Methods 0.000 title claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000003003 phosphines Chemical class 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000011877 solvent mixture Substances 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229910001510 metal chloride Inorganic materials 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 239000004753 textile Substances 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 3
- 125000001424 substituent group Chemical group 0.000 abstract 3
- 125000000962 organic group Chemical group 0.000 abstract 2
- 239000002216 antistatic agent Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000007942 carboxylates Chemical group 0.000 description 5
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 phospho Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- ZUXNHFFVQWADJL-UHFFFAOYSA-N 3,4,5-trimethoxy-n-(2-methoxyethyl)-n-(4-phenyl-1,3-thiazol-2-yl)benzamide Chemical compound N=1C(C=2C=CC=CC=2)=CSC=1N(CCOC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 ZUXNHFFVQWADJL-UHFFFAOYSA-N 0.000 description 1
- 241000238366 Cephalopoda Species 0.000 description 1
- IVHVNMLJNASKHW-UHFFFAOYSA-M Chlorphonium chloride Chemical group [Cl-].CCCC[P+](CCCC)(CCCC)CC1=CC=C(Cl)C=C1Cl IVHVNMLJNASKHW-UHFFFAOYSA-M 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001307279 Suteria ide Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- XPYGGHVSFMUHLH-UUSULHAXSA-N falecalcitriol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@@H](CCCC(O)(C(F)(F)F)C(F)(F)F)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C XPYGGHVSFMUHLH-UUSULHAXSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TWXDDNPPQUTEOV-FVGYRXGTSA-N methamphetamine hydrochloride Chemical compound Cl.CN[C@@H](C)CC1=CC=CC=C1 TWXDDNPPQUTEOV-FVGYRXGTSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
-
- 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
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Production of novel phosphobetaines of general formula I
I
in which R1 and R2 each stand for organic groups having from 1 to 18 carbon atoms, and R1 or R2 may be identical with the substituent R, the substituent R being a radical of the general formula II
II
in which R3 and R4 each stand for organic groups having from 1 to 18 carbon atoms and/or hydrogen atoms, and R5 stands for a linear or branched alkyl group having from 1 to 4 carbon atoms, which may optionally have a halogen or hydroxylic group substituent attached thereto. The novel phosphobetaines are useful as antistatic agents for textile materials.
Production of novel phosphobetaines of general formula I
I
in which R1 and R2 each stand for organic groups having from 1 to 18 carbon atoms, and R1 or R2 may be identical with the substituent R, the substituent R being a radical of the general formula II
II
in which R3 and R4 each stand for organic groups having from 1 to 18 carbon atoms and/or hydrogen atoms, and R5 stands for a linear or branched alkyl group having from 1 to 4 carbon atoms, which may optionally have a halogen or hydroxylic group substituent attached thereto. The novel phosphobetaines are useful as antistatic agents for textile materials.
Description
The present invention relates to a novel group of phosphobetaines of the formula I
Rl R3 R4 R ~?p _ C - C - CO ~ I
R H H
in which Rl is methyl and R2 has the meaning of Rl 01` of R, R being a radical of the formula II
- CoOR5 II
H H
in which R3 is hydrogen and R4 is methyl or hydrogen, and R5 is alkyl of 1-4 carbons.
The invention also relates to a process for making the above phosphobetaines.
Phosphobetaines which contain ester groups in addition to the carboxylate group in the molecule have .
~ 7~
not been. described hereto~ore, The phospho'betaines described hereto~ora, in which the quaternary phosphon:ium ion is :ln-tramolecularly saturated `by means o~ a carboxylate ~roup~ are high-melting stable compounds~ As described in Houben-Weyl~
Methoden der Organischen Chemie~ vol O XII~1~ page 107 et seq (Georg Thieme V~rlag, Stuttgart~ 196~)~ these phosphobetaines are ~ormed 'by multlple stage reaction~
Trimethylphosphine~ ~or example, can be reacted wîth chloroacetic acid to gi-ve carbox,ymethyl~trimethyl phosphonium chloride which. can be converted to the corresponding phosphobetaine by treatment with moist silver oxide.
)~p+GlcH2cooH--~/ (C~ )3PCH2COOH 7 Cl~
~CH3)3P ~ CH2COO
Phosphonium salts from tert.iary phosphines and chloroacetic acid alkyl esters~ which are admixed with basic media, give the corresponding phosphine alkylenes ~ather than phosphobetaines containing a carbox~late group.
A further process wherein trishydrox~methylphosphine is additively combined with an aiB unsaturated car~oxylic acid in accordance with the ~ollowing reaction equation:
(HOCH2)3P -~ CH2 _ CH~COOH ~ (HOCH~P~CH2CH2COOe has been described in German Patent Speci~ication 1yO45,401~
Triphenylpho~phine has been shown to form an analogous compound ~c~. W. Ho~mann, Chem. Ber,~ 94 ~ 3 ~
1331-6 (1961)).
It has also 'been described that phosphobetaines o~
the following ~ormula R~P~CH2 CH-C00~ "
are obtained 'by reacting a tertiary phosph.ine with an . ' a,B~unsaturated carboxylic acid ester. T.hese, however~
are unstable phosphobetaines which undergo ~ur-ther reaction.with the resultant ~ormatiorl of polymers or phosphine alkylenes (M.~. Shaw and R. S~ Ward7 Topics in Phosphorus Chemistry, vol. 75 1~35 (197~))0 In e~fecting the same reacti.on L~ Horner~ W~ Jur~eleit and~
Ko KlUfpel (c~. Lie'bigs AmO Chem. 591, 108~117 (1~55~) obtained the corresponding polymeric products o~ a,B-unsaturated carboxylic acid esters. In other words~ the tertiary phosphines were found to act as polyrnerlzation .,~ . .
catalysts. The additive combination o:~ the compou~.ds with the resultant ~o:rma-tion o~ a phosphobetaine containing a carboxylate group has not 'been described heretoforeO
The processes described hereinabove ~or making phosphobetaines containing a car~oxylate ~roup are highly unsatisfactory inasmuch as they'call for the exclusive use of tertiary phosph.l.ne startlng materîals7 ~or which it is partially necessary to be first converted to phosphonium ~alts and :Eor the pho.sphonium salts to be then subjected to alkaline -treatment so as to o~tain the desired product.
In addition to this, the prior art methods can only 'be used for making phospho~etaines into which the ~ .
-- 4 ~
,, :
. . ' . .
carboxylate is introduced via a oa~;boxy~lic acid~ ~7B-unsaturated carboxyli.c aci.d alky1. esters hav0 'bee~ ~ound to react with tertia~y phosphines to glve phosphine alkylenes or po'lymersO Phosphobetaines containin~ a carboxylat~ group are not obtainable .in this marmerO
The present in~ention now ~expecte~ly prov.ides a process for making a novel group of phosphobetaines o~
general formula I ~hich comprises reacting one or more phosphines o~ general ~ormula III
~ ~5 \ P - H IXI
~/ , in which R3 has the meaning given above~ and R6 has the same meaning as R4 with the exception of :
hydrogen, with one or more a,~ unsaturated c~arbox~lic ...
acid esters of general formula I~
\ C = C ~ CoOR5 IV
H '~
in which R3~ R4 and R5 equally have the meanings given ~' hereinabove, the reaction 'being e~'~ected in a single stage in the presence o~ water or a solvent/wa-ter-mixture; and separating the resultin~ phosphobetaines from the reaction product obtained.
The novel phosphobetaines of the present invention are obtained in the ~orm of colorless, thermally stable and highly ~iscous liquids.
A highly unexpected result resides in the fact - 5 ~
.
.. , . , . ~. , that the present reac-t.ion o~ t,he .~ormula IV ~B~
unsaturated carboxylic acid esters entails subs-tantially no s.ide reactions, e~g. poLymerization or forma-tion o~
phosphine alkylenes and seconda,~y produc,t,s~
~ f'urther hi~hly unexpected. result resides in the :Eact that the reaction is easy to effect in a single reaction stage without any need to separate a tertiary ~hosphine intermedlate or hydrolyze a carboxylic acid ester group to the carboxylate group, and with the resultant ~o~mation of high yields of desirable phosphobetainesO me reaction should p~e:Eera~ly be e~fected in the presen,ce of a catalyst~
The useful catalysts primarily comprise chlorides 9 ~ulfates and acetates of metals, such as ca~mium~
nickel and cobalt~ The catalys-t should conveniently be used at a rate o~ 0,1 to 10 millimol? preferably 1 to .
5 millimo1~ based on the total mixture. It îs also preferable -to effect the reactlon at temperatures of O to 120C, more pre~erably 15 to 80CI
Apart from water, the reaction mixture may contain one or more ~'urther solvents which primarily include.
alcohols or acetonitrile, It is ~inally advantageous to effect the reaction under inert ga~$ e~g. nitrogen~
The phosphobetaines obtained by the process o~
this invention are ~ery pure (9~99 ~). They are obtained in good yieLds a~ter disti-L:Lative removal of the water or water/solvent-mixture~
The quantitative ratio of the reaction eomponents is variable within wide lim.its and does not materially influence the course o~ the reaction, It i.s good - 6 ~
~ .
practice, however, to use the ~ormula III and ~ormula :LV reac-tan-ts in the stoi.chiometric proportions necessary for the formation of the :~or~lula X phosphobe-ta.irles.
In accordance with an advantageous ~eatur~ of the present process the ~ormula IV a~B-unsaturated carboxylic acid ester is introduced together with the catalyst into an aqueous phase9 which may be water or a water/solvent-mixture, the fo~mula III phosphine is added there~o, the whole is reacted at 0 to 120C, the resulting reaction solution ~is allowed to stand ~or a period of 2 to 3 hours, and the phosphobetaine is separated ~rom.the sol~ent.
The process of the present .inverltion compare.s ve~
favorably with the~rior art methods, principally in respect o~ the following points: It is a single stage reaction,~which is easy to ca.rry out without any ~eed to isolate intermediates~ and it produces readily separable, uni~orm and very pure final products in good yields.
The only by-product obtained .s -the alcohol ~corresponding to t~e for~ula IV corQ~ound) which can be separated together wi.th the solven-t~
The products o~ -the present invention a~e~or .
example, suitable ~or use ln imp~rtln~ antistatic properties to textile materia:ls.
EXAMPLE 1:
, CH2cH2cooc~I3 C~I - P/CH2CH2CO~ .
C~2cH2coocH~ .
: - 7 ~
.... . ._~
An agit~.tor provided apparatus scavenged w.ith nitrogen was charged with 87 g ~1 mol) of methyl acrylate in. 200 ml o~ water ~nd wlth 1 g o~ CdCl2 ~
Rl R3 R4 R ~?p _ C - C - CO ~ I
R H H
in which Rl is methyl and R2 has the meaning of Rl 01` of R, R being a radical of the formula II
- CoOR5 II
H H
in which R3 is hydrogen and R4 is methyl or hydrogen, and R5 is alkyl of 1-4 carbons.
The invention also relates to a process for making the above phosphobetaines.
Phosphobetaines which contain ester groups in addition to the carboxylate group in the molecule have .
~ 7~
not been. described hereto~ore, The phospho'betaines described hereto~ora, in which the quaternary phosphon:ium ion is :ln-tramolecularly saturated `by means o~ a carboxylate ~roup~ are high-melting stable compounds~ As described in Houben-Weyl~
Methoden der Organischen Chemie~ vol O XII~1~ page 107 et seq (Georg Thieme V~rlag, Stuttgart~ 196~)~ these phosphobetaines are ~ormed 'by multlple stage reaction~
Trimethylphosphine~ ~or example, can be reacted wîth chloroacetic acid to gi-ve carbox,ymethyl~trimethyl phosphonium chloride which. can be converted to the corresponding phosphobetaine by treatment with moist silver oxide.
)~p+GlcH2cooH--~/ (C~ )3PCH2COOH 7 Cl~
~CH3)3P ~ CH2COO
Phosphonium salts from tert.iary phosphines and chloroacetic acid alkyl esters~ which are admixed with basic media, give the corresponding phosphine alkylenes ~ather than phosphobetaines containing a carbox~late group.
A further process wherein trishydrox~methylphosphine is additively combined with an aiB unsaturated car~oxylic acid in accordance with the ~ollowing reaction equation:
(HOCH2)3P -~ CH2 _ CH~COOH ~ (HOCH~P~CH2CH2COOe has been described in German Patent Speci~ication 1yO45,401~
Triphenylpho~phine has been shown to form an analogous compound ~c~. W. Ho~mann, Chem. Ber,~ 94 ~ 3 ~
1331-6 (1961)).
It has also 'been described that phosphobetaines o~
the following ~ormula R~P~CH2 CH-C00~ "
are obtained 'by reacting a tertiary phosph.ine with an . ' a,B~unsaturated carboxylic acid ester. T.hese, however~
are unstable phosphobetaines which undergo ~ur-ther reaction.with the resultant ~ormatiorl of polymers or phosphine alkylenes (M.~. Shaw and R. S~ Ward7 Topics in Phosphorus Chemistry, vol. 75 1~35 (197~))0 In e~fecting the same reacti.on L~ Horner~ W~ Jur~eleit and~
Ko KlUfpel (c~. Lie'bigs AmO Chem. 591, 108~117 (1~55~) obtained the corresponding polymeric products o~ a,B-unsaturated carboxylic acid esters. In other words~ the tertiary phosphines were found to act as polyrnerlzation .,~ . .
catalysts. The additive combination o:~ the compou~.ds with the resultant ~o:rma-tion o~ a phosphobetaine containing a carboxylate group has not 'been described heretoforeO
The processes described hereinabove ~or making phosphobetaines containing a car~oxylate ~roup are highly unsatisfactory inasmuch as they'call for the exclusive use of tertiary phosph.l.ne startlng materîals7 ~or which it is partially necessary to be first converted to phosphonium ~alts and :Eor the pho.sphonium salts to be then subjected to alkaline -treatment so as to o~tain the desired product.
In addition to this, the prior art methods can only 'be used for making phospho~etaines into which the ~ .
-- 4 ~
,, :
. . ' . .
carboxylate is introduced via a oa~;boxy~lic acid~ ~7B-unsaturated carboxyli.c aci.d alky1. esters hav0 'bee~ ~ound to react with tertia~y phosphines to glve phosphine alkylenes or po'lymersO Phosphobetaines containin~ a carboxylat~ group are not obtainable .in this marmerO
The present in~ention now ~expecte~ly prov.ides a process for making a novel group of phosphobetaines o~
general formula I ~hich comprises reacting one or more phosphines o~ general ~ormula III
~ ~5 \ P - H IXI
~/ , in which R3 has the meaning given above~ and R6 has the same meaning as R4 with the exception of :
hydrogen, with one or more a,~ unsaturated c~arbox~lic ...
acid esters of general formula I~
\ C = C ~ CoOR5 IV
H '~
in which R3~ R4 and R5 equally have the meanings given ~' hereinabove, the reaction 'being e~'~ected in a single stage in the presence o~ water or a solvent/wa-ter-mixture; and separating the resultin~ phosphobetaines from the reaction product obtained.
The novel phosphobetaines of the present invention are obtained in the ~orm of colorless, thermally stable and highly ~iscous liquids.
A highly unexpected result resides in the fact - 5 ~
.
.. , . , . ~. , that the present reac-t.ion o~ t,he .~ormula IV ~B~
unsaturated carboxylic acid esters entails subs-tantially no s.ide reactions, e~g. poLymerization or forma-tion o~
phosphine alkylenes and seconda,~y produc,t,s~
~ f'urther hi~hly unexpected. result resides in the :Eact that the reaction is easy to effect in a single reaction stage without any need to separate a tertiary ~hosphine intermedlate or hydrolyze a carboxylic acid ester group to the carboxylate group, and with the resultant ~o~mation of high yields of desirable phosphobetainesO me reaction should p~e:Eera~ly be e~fected in the presen,ce of a catalyst~
The useful catalysts primarily comprise chlorides 9 ~ulfates and acetates of metals, such as ca~mium~
nickel and cobalt~ The catalys-t should conveniently be used at a rate o~ 0,1 to 10 millimol? preferably 1 to .
5 millimo1~ based on the total mixture. It îs also preferable -to effect the reactlon at temperatures of O to 120C, more pre~erably 15 to 80CI
Apart from water, the reaction mixture may contain one or more ~'urther solvents which primarily include.
alcohols or acetonitrile, It is ~inally advantageous to effect the reaction under inert ga~$ e~g. nitrogen~
The phosphobetaines obtained by the process o~
this invention are ~ery pure (9~99 ~). They are obtained in good yieLds a~ter disti-L:Lative removal of the water or water/solvent-mixture~
The quantitative ratio of the reaction eomponents is variable within wide lim.its and does not materially influence the course o~ the reaction, It i.s good - 6 ~
~ .
practice, however, to use the ~ormula III and ~ormula :LV reac-tan-ts in the stoi.chiometric proportions necessary for the formation of the :~or~lula X phosphobe-ta.irles.
In accordance with an advantageous ~eatur~ of the present process the ~ormula IV a~B-unsaturated carboxylic acid ester is introduced together with the catalyst into an aqueous phase9 which may be water or a water/solvent-mixture, the fo~mula III phosphine is added there~o, the whole is reacted at 0 to 120C, the resulting reaction solution ~is allowed to stand ~or a period of 2 to 3 hours, and the phosphobetaine is separated ~rom.the sol~ent.
The process of the present .inverltion compare.s ve~
favorably with the~rior art methods, principally in respect o~ the following points: It is a single stage reaction,~which is easy to ca.rry out without any ~eed to isolate intermediates~ and it produces readily separable, uni~orm and very pure final products in good yields.
The only by-product obtained .s -the alcohol ~corresponding to t~e for~ula IV corQ~ound) which can be separated together wi.th the solven-t~
The products o~ -the present invention a~e~or .
example, suitable ~or use ln imp~rtln~ antistatic properties to textile materia:ls.
EXAMPLE 1:
, CH2cH2cooc~I3 C~I - P/CH2CH2CO~ .
C~2cH2coocH~ .
: - 7 ~
.... . ._~
An agit~.tor provided apparatus scavenged w.ith nitrogen was charged with 87 g ~1 mol) of methyl acrylate in. 200 ml o~ water ~nd wlth 1 g o~ CdCl2 ~
2 1/2 H20O 20 g ~0.4 mol~ of methyJ.pho,sphine was added.
together with nitrogen as an .ine-~t gas within 1 h.our.
The temperature was kept within the range of 24 to 30C by cooling from the outside~ ~n intermediate precipitate became completely dissolved during the post reaction period of 3 hours~ The sol~ent was distillatively separated and a c~lorles,s highly viscous liquid remained behind.
The yield was 90 % of the theoretical~
Analysis: Found: Calculated:
P ~.9 % 10~6 %
'' ';''''''- .
CH3 - P - CH2CH2C00~
CH2CH2COOC~Hg Butyl acrylate was reacted with methylphosphine in the manner described in Example 10 The yield was 97 ~o.
Analysis: Found: Calculated:
P 8.0 % 8.23 %
E~
0/ CH2CH2COOC~I3
together with nitrogen as an .ine-~t gas within 1 h.our.
The temperature was kept within the range of 24 to 30C by cooling from the outside~ ~n intermediate precipitate became completely dissolved during the post reaction period of 3 hours~ The sol~ent was distillatively separated and a c~lorles,s highly viscous liquid remained behind.
The yield was 90 % of the theoretical~
Analysis: Found: Calculated:
P ~.9 % 10~6 %
'' ';''''''- .
CH3 - P - CH2CH2C00~
CH2CH2COOC~Hg Butyl acrylate was reacted with methylphosphine in the manner described in Example 10 The yield was 97 ~o.
Analysis: Found: Calculated:
P 8.0 % 8.23 %
E~
0/ CH2CH2COOC~I3
3 ) 2P
\ CH2CH~,COO~
103 g (~.2 mol) o~ meth~:l acxylate in 200 ml of ~ ' ~7~
water was reacted as described irl Example 1 with 3~5 g (0.62 mol) o~` dime-thylphosphine i~ -the presence of 005 g o~ CdCl2 o 2 1~2 H20. The ~olv0nt and low~boîling fractions were disti.~ed o~.t~ and a h:ighly v.iscous oi.l was obtained.
The yield ~as 96 ~ of the theorekical~
Analysis: Found: Calculateds P 13 o 5 % 1/-1706 %
~, ~CH2CH(CH3~COOCH3 CH3 ~ P ~ CH2CH(CH3)C0~9 SH~cH(cH3~cooH3 100 g ~1 mol~ of methyl methacrylate was reacted with 20 g (004 mol) of methylphosphine, in the manner described ln Example 1.
~he yield was 86 %.
~nalysis- Found: Calculatedo - P808 % 9~26 %
_ 9 ,, , . . : ,
\ CH2CH~,COO~
103 g (~.2 mol) o~ meth~:l acxylate in 200 ml of ~ ' ~7~
water was reacted as described irl Example 1 with 3~5 g (0.62 mol) o~` dime-thylphosphine i~ -the presence of 005 g o~ CdCl2 o 2 1~2 H20. The ~olv0nt and low~boîling fractions were disti.~ed o~.t~ and a h:ighly v.iscous oi.l was obtained.
The yield ~as 96 ~ of the theorekical~
Analysis: Found: Calculateds P 13 o 5 % 1/-1706 %
~, ~CH2CH(CH3~COOCH3 CH3 ~ P ~ CH2CH(CH3)C0~9 SH~cH(cH3~cooH3 100 g ~1 mol~ of methyl methacrylate was reacted with 20 g (004 mol) of methylphosphine, in the manner described ln Example 1.
~he yield was 86 %.
~nalysis- Found: Calculatedo - P808 % 9~26 %
_ 9 ,, , . . : ,
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Phosphobetaines of formula I
I
in which R1 is methyl and R2 has the meaning of R1 or of R, R being a radical of the formula II
II
in which R3 is hydrogen and R4 is methyl or hydrogen, and R5 is alkyl of 1-4 carbons.
I
in which R1 is methyl and R2 has the meaning of R1 or of R, R being a radical of the formula II
II
in which R3 is hydrogen and R4 is methyl or hydrogen, and R5 is alkyl of 1-4 carbons.
2. Phosphobetaine of the formula
3. Phosphobetaine of the formula
4. A process for making phosphobetaines of the formula I
in which R1 is methyl and R2 has the meaning of R1 or of R, R being a radical of the formula II
II
in which R3 is hydrogen and R4 is methyl or hydrogen, and R5 is alkyl of 1-4 carbons, which process comprises reacting phosphines of the formula III
III
in which R1 and R4 have the meanings given above, with an .alpha.,.beta.-unsaturated carboxylic acid of the formula IV
in which R3, R4 and R5 have the meanings given above, the reaction being effected in a single stage in the presence of water or a solvent/water-mixture, and separating the resulting phosphobetaines from the reaction product obtained.
in which R1 is methyl and R2 has the meaning of R1 or of R, R being a radical of the formula II
II
in which R3 is hydrogen and R4 is methyl or hydrogen, and R5 is alkyl of 1-4 carbons, which process comprises reacting phosphines of the formula III
III
in which R1 and R4 have the meanings given above, with an .alpha.,.beta.-unsaturated carboxylic acid of the formula IV
in which R3, R4 and R5 have the meanings given above, the reaction being effected in a single stage in the presence of water or a solvent/water-mixture, and separating the resulting phosphobetaines from the reaction product obtained.
5. The process as claimed in claim 4, wherein the reaction is effected in the presence of a catalyst.
6. The process as claimed in claim 5, wherein metal chlorides, sul-fates or acetates are used as the catalyst.
7. The process as claimed in claim 6, wherein the catalyst is a chloride, sulfate or acetate of cadmium, nickel or cobalt.
8. The process as claimed in claim 5, wherein the catalyst is used at a rate of 0.1 to 10 millimol, based on the total mixture.
9. The process as claimed in claim 8, wherein the catalyst is used at a rate of 1 to 5 millimol, based on the total mixture.
10) The process as claimed in claim 4, wherein the reaction is effected at temperatures of 0 to 120°C.
11) The process as claimed in claim 10, wherein the reaction is effected at temperatures of 15 to 80°C.
12) The process as claimed in claim 4, wherein the solvent is an alcohol, acetonitrile or a mixture thereof.
13) The process as claimed in claim 4 wherein the phosphobetaine is separated from the reaction mixture by distillative removal of the solvent.
14) The process as claimed in claim 4, wherein the formula III phosphine and the formula IV .alpha.,.beta.-unsaturated carboxylic acid ester are reacted in the stoichiometric proportions necessary for the formation. of the formula I phosphobetaine.
15) The process as claimed in claim 4, wherein the formula IV .alpha.,.beta.-unsaturated carboxylic acid ester is introduced together with the catalyst into an aqueous phase being water or a water/solvent-mixture, the formula III phosphine is added thereto, the whole is reacted at 0 to 120°C, the resulting reaction solution is allowed to stand for a period of 2 to 3 hours, and the phosphobetaine is separated from the solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752540260 DE2540260C2 (en) | 1975-09-10 | 1975-09-10 | Phosphor betaines and processes for their preparation |
| DEP2540260.2 | 1975-09-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1117970A true CA1117970A (en) | 1982-02-09 |
Family
ID=5956062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000259646A Expired CA1117970A (en) | 1975-09-10 | 1976-08-23 | Phosphorbetaines and process for making them |
Country Status (8)
| Country | Link |
|---|---|
| BE (1) | BE845986A (en) |
| CA (1) | CA1117970A (en) |
| CH (1) | CH619966A5 (en) |
| DE (1) | DE2540260C2 (en) |
| FR (1) | FR2323697A1 (en) |
| GB (1) | GB1517074A (en) |
| IT (1) | IT1076809B (en) |
| NL (1) | NL7610026A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1200295B (en) * | 1964-03-05 | 1965-09-09 | Bayer Ag | Process for the preparation of Triarylphosphinopropionsaeurebetainen |
| US3504024A (en) * | 1966-08-23 | 1970-03-31 | Procter & Gamble | Phosphonio carboxylates |
-
1975
- 1975-09-10 DE DE19752540260 patent/DE2540260C2/en not_active Expired
-
1976
- 1976-08-23 CA CA000259646A patent/CA1117970A/en not_active Expired
- 1976-08-23 CH CH1068076A patent/CH619966A5/en not_active IP Right Cessation
- 1976-08-26 GB GB3555176A patent/GB1517074A/en not_active Expired
- 1976-09-08 IT IT5117076A patent/IT1076809B/en active
- 1976-09-09 BE BE170460A patent/BE845986A/en not_active IP Right Cessation
- 1976-09-09 NL NL7610026A patent/NL7610026A/en not_active Application Discontinuation
- 1976-09-10 FR FR7627377A patent/FR2323697A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IT1076809B (en) | 1985-04-27 |
| GB1517074A (en) | 1978-07-12 |
| DE2540260A1 (en) | 1977-03-17 |
| FR2323697A1 (en) | 1977-04-08 |
| CH619966A5 (en) | 1980-10-31 |
| NL7610026A (en) | 1977-03-14 |
| BE845986A (en) | 1977-03-09 |
| DE2540260C2 (en) | 1984-03-01 |
| FR2323697B1 (en) | 1979-06-22 |
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