CA1079745A - Process for preparing 1,2-oxa-phospholanes - Google Patents

Process for preparing 1,2-oxa-phospholanes

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CA1079745A
CA1079745A CA255,707A CA255707A CA1079745A CA 1079745 A CA1079745 A CA 1079745A CA 255707 A CA255707 A CA 255707A CA 1079745 A CA1079745 A CA 1079745A
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carbon atoms
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acid
methyl
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Hans-Jerg Kleiner
Manfred Finke
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Hoechst AG
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    • 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
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
    • 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)]
    • C07F9/34—Halides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only

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  • Organic Chemistry (AREA)
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  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

PROCESS FOR PREPARING 1,2-OXA-PHOSPHOLANES

Abstract of the disclosure:

A process for the preparation of 2,5-dioxo-1,2-oxa-phospholanes having general formula (I) (I) wherein R1 represents an alkyl group being optionally substi-tuted and having up to 18 carbon atome, a cycloalkyl group having up to 8 carbon atoms, an alkenyl group having up to 8 carbon atoms, an aryl group having up to 14 carbon atoms being possibly sub-stituted by lower alkyl groups, by alkoxy groups, by halogen or by alkylated or dialkylated amino groups, or which represents an aralkyl group having up to 15 carbon atoms and being possibly substituted in the same way as the aryl group, wherein R2 stands for a lower alkyl group or hydrogen and R3 stands for a lower alkyl radical, a phenyl radical being possibly substituted by halogen or lower alkyl groups, for a benzyl radical or for hydrogen, which comprises reacting in a single reaction vessel a selected dihalogenophospine with an equimolar quantity of a selected .alpha.,.beta.-unsaturated acid and an equivalent quantity of a selected acid compound such as acetic acid,propionic acid, sulfonic acid, dimethyl-phosphinic acid, methyl-ethyl-phosphinic acid and methyl-ethyl-phosphinic acid - isobutyl ester. The process is a one-vessel reaction accomplished without the isolation and purification of intermediate products and,in addition to the primary product produces,other useful reaction products.

- 1a -

Description

107~7~5 -_ ,:
It is a known fact that 2-chloroformylethyl~phosphinic acid chlorides which are easily accessible from alkyldichlorophosphines and ~,B-unsaturated carboxylic acids, may be cyclized with acetanhydride to yield 2,5-dioxo-1,2-oxa-phospholanes, acetyl-chloride being formed as bv-product (V.K.Char~rullin, I.I. Sob-cuk and A.N. Pudovik, Z. obsc. Chim. 37, 710 ~1967), V.K. Chaj-rullin, R.M. Kondrat'eva and A.N. Pudovik, Z. obsc. Chim. 38, 288 (1968)):

CH ~x CH3PCl2 + CH2 = CCOOH ~ / PCH2CHCOCl Rx Cl O
0 0 CH3 "

ClCCH-CH2P / (C~13CO)2O r P - CH3 Rx Cl - 2 CH3COC] ~ 0 Rx = H~ CH3 ,`
Publications of the same authors have made known further-2n more the cyclization of 2-chloroformyleth~l-phosphinic acid chlorides by means of 1 mole of ethanol or acetic acid to yi~ld phospholanes.
These processes have the disadvantage that 2-chloroformyl-ethyl-phosphinic acid chlorides have to be prepared in a sepa-rate processing step, then purified by distillation and finally~in a second processing step, to be submitted to reaction with the cyclization agent to yield the corresponding phospholanes. ~
It has now been found that 2,5-dioxo-1,2-oxa-phospholanes ~ -29 having general formula ~

;, , - .

.. 107979~
"

R2-- P -- R~
R3 ~ (I) wherein Rl represents an alkyl group, optionally substituted, having up to 18 carbon atoms, preferably from l to 12, especially from l to 4 carbon atoms, which may carry preferably as three, but especial1y one substituent halogen, especially chlorine, or a cycloalkyl group having up to 8 carbon atoms, especially cyclohexyl or cyclopentyl,an alkenyl group having up to 8 carbon atoms, especially vinyl or allyl, an aryl group hav.ing up to l~ carbon atoms, especially phenyl, which may be substituted - preerably up to twice - by low alkyl groups having up to 4 carbon atoms, low alkoxy groups having up to 4 carbon atoms, halogen or by alkylated or dialkylated amino groups, or which represents an aralkyl group being substituted in the same way as the aryl group, and having up to lS carbon atoms, especially benzyl, wherein R2 stands for an alkyl group having up to 4 carbon atoms, preferably methyl, or hydrogen and wherein R3 stands for an alkyl radical having up to 4 carbon atoms, especially methyl, a phenyl radical which may be substituted up to three times, preferably once or twice, by halogen, preferably chlorine, or low alkyl groups having up to 4 carbon atoms, preferably methyl, for a benzyl radical or for hydrogen, preferably at least one of the radicals R , R~ represents a hydrogen atom, may be ob-tained by reacting dihalogenophosphines of general formula (II) 10797~5 ~IOE 75/F 172 R1 _ p / ~II) \X

wherein R1 has the same meaning as in formula ~I) and wherein X stands for chlorine or bromine, preferably for chlorine, with an equimolar quantity of an ~ ,~-unsaturated acid of formula (III) CH=CH-COOH (III) wherein R2 and R3 have the same meaning as in ormula (I), and simul~aneously, especially as a mixture, with an equi~ale~nt q~1an- ;
tity of a compound having formula (IV) R4 - OH (IV) wherein R4 represents hydrogen or an acyl radical having from 2 ~
to 12, preferably from 2 to 8, especially from 2 to 4 carbon atoms, being possibly substituted by a hydroxy gxoup in ~ - or ~ ~position or being substituted from once to three times by halogen, es~ecially by chlorine, or by a carboxyl group, or ~here-in R4 represents the radical -CO-COOH, an alkyl-sulfonyl radi-cal, phenyl-sulfonyl radical, phenalkyl-sulEonyl radical or ~`
alkylphenyl-sulfonyl radical having up to 12 carbon atoms, pre-ferably up to 8 carbon atoms, or wherein R represents a radical of formula (IVa) R5 0 ~ ~
\ " :'., \ p_ (IVa) R6 . ~ ' .
29 wherein R5 represents an alkyl radical having up to 12 carbon - 4 - ~;

~79745 HOE 75/F 172 atoms, preferably up to 8 carbon atoms, especially up to 4 car-bon atoms, being possibly substituted from one to three times, especially once, by halogen, especially by chlorine, a cyclo- .
alkyl radical having up to 8 carbon atoms, especially cyclo-pentyl or cyclohexvl, an alkenyl radical having from 2 to 12, preferably from 2 to 6 carbon atoms, especially vinyl or allyl and wherein R6 has the meaning as specified for R5 or is stand-ing for a carboxylic acid group having from 2 to 4 carbon atoms or for HO(CH2)~- or for HO(CH2)4-, or with an equivalent quantity of a compound having formula (V), R a \ P - ~ R7 ~6 /

~herein ~ and R have the meanin~ as in formula (IVa) and where-in R7 has the meaning of R5 or represents a group of formula (IVa), or with an equivalent quantity of mixtures of compounds having formulae (IV) and (V) and by isolati.ng the reaction products.
By equivalent quantities, calculated on 1 mo].e of the start-ing components having ~ormulae (II) or (III) are to be under-~tood the quotients of molecu1ar wei~ of the compounds havil1g formulae (IV) or (V), n representing the number of functional groups in the molecule of the compounds having formulae (IV) or (V). Functional groups in respect to the present inventicn may be: carboxyl groups, sulfonic acid groups, phosphinic acid groups, phosphinic acid ester groups and phosphinic acid anhy-dride groups.
The process according to the invention does not only yield 29 the desired 2,5-dioxo-1,2-oxa~phospholanes depending on the nalure :

~ HOE 75/F 172 of the initial materials of formulae tIV) or ~V), but as well the reaction products from these latter. Thus are obtained, besides phospholanes, for example acyl halides, sulfonyl hali-des, and phosphinie acid halides, which may be isolated and ob-tained in its pure state. Moreover, in the ease of eompounds being apt to eyclization such as 3- or 4-hydroxy-alkane car-boxylic aeid laetones and in the case of 3- or 4-hydroxy-alkyl-phosphinie aeids or its esters phostones are formed which may also be separated and obtained in its pure state. By doubling ;
the employed quantity of eompounds having formulae (IV) or (V) it is possible in some eases, of course, to obtain still further produets, i.e. in the ease o s~1eeinie aeid or glu~arie ~eid their inner anhydrides, in the ease o phosphinie aeids or phosphinie aeid esters the eorresponding phosphinic acid anhy-drides.
The following reaction schemes as per the invention may ex- -plain more clearly the reactions of dihaloyenophosphines with d,B-unsaturated earboxylic acids and compounds hav}ng formulae tIV) or tV): -1) R1PX2 ~ ~H=C~ACOOH + R-COOH ~ R2 P - R1 ~pQO~
R3 ~ -.. . . :
. O O
X2 + Cl~ CIHOOOH + HCCH2CH2CH2CR~ R1 + ~ o + 2 HX

~. . .

~L~7979L5 HC)E 75~F 172 3) R1PX2 + Cll=CHCO~H + ~ R --> ~ R6~

~5 0 o O
4) ~1PX2 ~ ~COOM t >PoR7 ~ R rP - R1 + ~ P5 R R HO (CH2) 3 R3/y ~ R7X + ~IX

R O '' 1 R5 0 0 ~1~5
2 , . ? ~;o 6> \ 6 + 2 RX

S~-risingly, the dihalogenophosphines ean be reacted with a mixture of a ~ ,~unsaturated carboxylic acid and a ccmpound of form~1la ~IV) or (V) in a reactlon.without i~o~.ation of inter mediate produets to yield 2,5-dioxo-1,2-oxa-phospholan~s, thou~h dihalogenophosphines are also r~actirl~3 in the a~ser)ce of .~
unsaturated earboxylic acids with compounds of formulae (IV) or (V), while forming such products which do not participate in any reaction with ~,B-unsaturated earboxylic aeids under the re-action conditions of the process aecording to the invention.
Thus, earboxylie aeids such as aeetic acid, propionic acid and butyric acid react even at a temperature ~elow room temperature with alkyl diehlorophosphine to yield 1-hydroxy-alcane-l,1-bis-_ 7 _ ~7974~ HOE 75/F 172 alkyl-phosphinic acids (German Offenlegungsschrift 2.153.998), which do not cyclize with a, ~-unsaturated carboxylic acids to yield 2,5-dioxo-1,2-oxa-phospholanes.
The reactions according to the invention as described per the a.m. fig. 1) - 5) may be performed, of course, in two processing steps as well as, namely first the addition of a, ~-un-saturated carboxylic acid, subsequently the cyclization, in the same reaction vessel.
It is to be considered a special advantage of the process according to the invention, that the so-called "one-vessel-xeaction"
(= reaction without isolation of intermediate products) does away with cumbersome processing steps such as isolation and puri~ic~tion of an intermedi~te product so that -the all-over re-action periods may be cut down substantially. Moreover, the a.m.
halides, anhydrides and derivatives of phosphinic acid can be prepared by choosing a suitable compound of formulae (IV) or (V) and the stoichiometric ratio of these compounds to the molar number of the two other reaction partners.
There may be utilized according to the invention as suitable dihalogenophosphines of ~ormula (II) which are prepared according to known methods, ~or example:
Methyldichloro-phosphine, ethyldichloro-phosphine, propyldichloro-phosphine, butyldichloro-phosphine, dodecyldichloro-phosphine, chloromethyldichloro-phosphine, vinyldichloro-phosphine, cyclo-hexyldichloro-phosphine, benzyldichloro-phosphine, phenyldi-chloro-phosphine,p-chlorophenyldichloro-phosphine and the cor-responding aibromo-phosphines.
Suitable a,~-unsaturated carboxylicacids of formula (III) to be employed are for example acrylic acid, methacrylic acid, . . .

crotonic acid, l-ethyl-acrylic acid, l-phenyl-acrylic acid.
As suitable compounds of formulae (IV) or (V) may be con-sidered for example:
Acetic acid, propionic acid, butyric acid, caproic acid, mono-chloro-acetic acid, trifluoro-acetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, ~ -hydroxy-butyric acid, methane-sulfonic acid, ethane-sulfonic acid, propane-sulfonic acid, benzene-sulfonic acid, dimethyl-phosphinic acid, ethyl-methyl-phosphinic acid, diethyl-phosphinic acid, methyl-propyl-phosphinic acid, methyl-propyl-phosphinic acid, methyl-dodecyl-phosphinic acid, diphenyl-phosphinic acid, dimethyl~phosphinic ac.id-ethyl ester, dirnethyl-phosphinic acid-2-chloroethyl ester, m~thyl-eth~l-phosphin.ic acid .isobutyl e~ter, methyl-hexyl-phosphinic acid-butyl ester, hydroxymethyl-methyl-phosphinic acid, 3-hydroxypropyl-methylphosphinic acid, dimethyl-phosphi-nic acid-anhydride, methyl-ethyl-phosphinic acid-anhydride, methyl-butyl-phosphinic acid-anhydride, methyl-phenyl-phosphi-nic acid-anhydride, diphenyl-phosphinic acid-anhydride.
Preferred compounds are acetic acid, propionic acid, sul-fonic acids, dimethyl-phosphinic acid, methyl-ethyl-phosphinic acid and methyl-ethyl-phosphinic acid-isobutyl ester.
Generally, the process according to the invention, is car-ried out in such a way that a mixture of an ~,~-unsaturated carboxylic acid and of a compound of formulae (IV) or (V) is added dropwise to the dihalogenophosphines. However, it is also possible to add the dihalogenophosphines to a mixture of the two other reaction partners. The dihalogenophosphines and the ~ unsaturated carboxylic acids are utilized in equimolar quantities, whilst the stoichiometric ratio of the compounds 30~j of formulae (IV) or (V) to the other reaction partners depends H-~E_75/F I 7 '~

on the fact, whether e.g. halides or - especially in the case of bifunctional compounds - lactones, carboxylic acid-anhydrides or phosphinic acid-anhydrides are desirable by-products. Ac-cordingly, the molar ratio of dihalogenophosphines or ~,.3-un-saturated carboxvlic acids to the m~n~flln~ n~1 c~mno~ln~c ~f formulae (IV) and (V) may therefore be either 1:1 or 1:2, whilst - comparatively - the bifunctional compounds of formulae (IV) and (V) may be employed at a molar ratio of 1:1 or 0. 5 :1 to the other reaction par-tners.
As solubilizers or as diluents may be added to the dihalo-genophosphines or to the two othel- reaction par~ners inert sol-vents, for ex~mple aliphatic, cycloaliph~tic, aroma~ic ~r ar-~raliphatic hy~rocarbons such as xyl~nc~, chlorobenzene, toluene, chlorotoluene, dichlorobenzene, benzene fractions boili~1g at a higher temperature, carbon chlorides such as methylene chloride, chlc,roform, 1,2-dichloroethane, 1,2-dichloropropane, ethers such as tetrahydrofurane, dioxane, isopropyl ether, di-n-butyl ether, dimethoxy ethane, polyethylene-glycol-dialkyl ether and poly-prop~lene glycol-dialkyl ether. However, preerence is ~iven :~0 to ca~ry O~lt the proces~ o~ the irlvention in th~ absen~e of inert solvents.
The reaction temperature ought to ~e approximateiy f rom -20C to +160C, preferably from O~C to +lO0C, especiall~ flor;~
+15C to+80C. There is no need to keep the reaction tempera-ture at a constant level by exterior cooling devices. When operating without a solvent it may be rather advantageous to allow the reaction temperature to climb to the melting point of ' the phospholane so as to reduce the viscosity of the reaction 29 mixture.

~79745 HOE 75~F 1-/2 The reaction time varies generally from a~ou~ 2 to 6 hours~
The reaction mixture is subsequently stirred for approximately half an hour at a temperature of from 100 to 130C under normal pressure and furthermore stirred for half an hour at about 130 S to 200C under water jet vacuum.
The 2,5-dioxo-1,2-oxa-phospholanes may generally be easily separated from the other reaction products by fractional distil-lation. Highly volatile reaction products are elimina~ed al-ready while stirring additionally under normal pressure or under water jet vacuum. It is also possibl~, however, to se-parate and purify the reaction mixture by extraction with inert solvcnts or by recrystal:Lization.
Th~ yield~ in 2,5-dioxo-1,2-oxa-phospholanes obtained r~-present about 70 - 80 % of the theoretical yield, calculated on the dihalogenophosphines of formula (II) being employed. 2,5-di-oxo-1,2-oxa-phospholanes are good flame-retardants which may be utilized ror preparing barely inflar~nable, linear polyesters.
They represent furthermore valuable intermed;.ate products ~hi.ch may be further processed e.g. to yield flameproofing agents. ~ ;
The following Examples illustrate tlle invention:
E X A M P L E 1:
2~methyl-2,5-dioxo-1,2-oxa-phospl1olar.e bas2d _n _ ethyldichloro-phosphine, acrylic acid and water A mix~ure of 225 g (3.12 mole) of acrylic acid and 56 g (3.12 mole) of water is added dropwise at 20 - 25C to a so-lution of 365 g (3.12 mole) of methyldichlorophosphine in 600 ml of methylene chloride. During this operation a strong current . of hydrogen chloride is discharged. The solvent is distilled 29 off and subsequently heated under water jet vacuum for about HOL~ 75/'~ 1 72 ~079745 , 4 hours to 130 - 150C. After distillation in a film evapo-rator (boiling point at 1 mm Hg: 164 - 170C) 32? g of 2-methyl-2,5-dioxo-1,2-oxa-phospholane are obtained represent-ing a yield of 77 % of the theoretical yield calculated on methyldichlorophosphine.
E X A M P L E 2: ;
2-methyl-2,5-dioxo-1 2-oxa-phospholan _ ased on methyldichloro-pho~sphine~ acrylic ac d and acetic acid A mixture of 72 g (1 mole) of acrylic acid and 60 g (1 mole) of glacial acetic acid is added drop~ise at 25 - 30C to 117 ~ (1 mole) of methyl-dichlorophosphine. A~ter termination of the dropwise addition, the reaction solution is heat~d to 60 - 100C, while acetyl chloride (57 g) is di~ttilled off and a strong current of hydrogen chloride i5 discharged. In order to eliminate the residual quantities of hydrogen chloride, heat-ing takes place under water jet vacuum to an internal tempera-ture of 150C. The crude phospholane is purified by high vacu-um distillation. 98 g of 2-methyl-2,5-dioxo-1,2-oxa-phospho-lane ~boiling point1 5: 169C) are obtained, representing a yi~ld o~ 73 ~ of the ~heo~etical yield.
E X M P L E 3:
2-m~ h~ 2 ~-dio~o-1 2-oxa-phost~ho]alle based Ol1 n thy~lc1icl1l ro-phosphine acrylic acid and propionic acid A mixture of 36 g (0.5 mole) of acrylic acid and 37 g (0.5 mole) of propionic acid is added dropwise at 20 - 30C
to 58.5 g (0.5 mole) of methyldichlorophosphine. After termi-nation of the dropwise addition the reaction solution ;s heated to 80 - 130C, whi1e propionic acid ~hloride (36 g) is distil-29 led off and hydrogen chloride dischar~ed. Subsequent1y heating HorJ 75/F 1/2 10797~5 takes place under water jet vacuum to 150 - 16Q~C so as to eliminate the residual quantities of hydrogen chloride. After high vacuum distillation of the crude phospholane 47 g of 2-methyl-2,5-dioxo-1,2-oxa-phospholane (boiling point at 0.7 m~ ~g: 1'0 -- 15~C) are obtained, ccr espo.. d ng to ~ yicld of 70~ of the theoretical yield.
E X A M P L E 4:
2-methyl-2,5-dioxo-1 ! 2-oxa-phospholane Oll methyldichlorophos-phine, acrylic acid and propane-sulfonic acid A mixture of 36 g (0.5 mole) of acrylic acid and 62 g (0,5 mole) of propane-sul~onic acid is added dropwise to 58.5 g (0.5 mole) of methyldichloro~ho3phine A-t 20 - 30C. After termination of the dropwise addikion, the temperature l~s 510w-ly increased to 100C, while hydrogen chloride is discharged.
Subsequently, propane-sulfonic acid chloride (18 g) is distil-led off under water ]et vacuum at an internal tempsrature of from 120 - 160C. The high vacu~m distillation of the residve yields 51 g of 2-rnethyl-2,5-dio~o-1,2-oxa-phospholane tboiling point at 2 mm Hg: 185" - 190C), representing a yield of 7~.4 Or. the th~oretical yield.
E X A M P L E 5:
t~ ~ based on meth ,vldicl oro-phosphine, acrylic acid and methyl-ethyl-phosphinic aci~
A mixture of 36 g ~0.5 mole) of acrylic acid and 54 g (0.5 mole) of methyl-ethyl-phosphinic acid is added drop~ise at 20 - 30C to 58.5 g (0.5 mole) of methyldichlorophosphine.
After termination of the dropwise addition, the temperature is slowly increased to 100 - 120C, while hydrogen chloride is 29 discharged. Subsequently 40 g of methyl-ethyl-phosphinic acid-~, ;

.

HOE 75/F' 172 ~07~4S
;'.
chloride are distilled of~ under water jet vacuum at an internal temperature of 130 - 170C. The high vacuum distillation of the residue yields 47 g of 2-methyl-2,5-dioxo-1,2-oxa-phospho~
lane (boiling point at 1.3 mm Hg: 165~ - 168C), corresponding to a yield of 70 % of the theoretical yield.
E X A M P L E 6:
2-m~thyl-2,5-dioxo-1~2-oxa-phospho]ane based on methyldichloro-phosphine, acrylic acid and meth~l-ethyl-phosphinic acid-an-hydride A mixture of 36 g (0.5 mole) of acrylic acid and 99 g (0.5 mole) of methyl-ethyl-phosphinic acid-anhydride i5 added dropw~8~ to 58.5 g (0.5 mole) of methyldichloro-phosphine ~t 20 - 40C. After termina~ion of the dropwise addition ctir-ring takes place for 15 minutes at 80 - 100C. Subsequently, 98 g of methyl-ethyl-phosphinic acid-chloride are distilled off under water jet vacuum at an internal temperature of 120 -160~C. The high vacuum distillation of the residue yields 49 g of 2-methyl-2,5-dioxo-1,2-oxa-phospholane, corresponding to a yield of 73 % of the theoretical yield.
E X A ~ P I, E 7:
, 2~methyl-2,5-dioxo-1,2-oxa-phospholane based on_methyldich]oro phosp]1in2, acr;~lic acici an~ r,1eth5~ tl1,l-pl1osphinic acid-i~;o-butyl ester A mixture of 36 y (0.5 mole) of acrylic acid and 76 y (0.5 mole) of methyl-ethyl-phosphinic acid-isobutyl ester is added dropwise to 58.5 g (0.5 mole) of methyldichloro-phosphine at 25 ~ 50C. After termination of the dropwise addition approxi-mately 30 g of isobutyl chloride are distilled off under normal 29 pressure. Sub~equently, methyl-ethyl~phosphinic acid-chloride - 14 ~

1079~45 HOE 75/E 17~

(about 26 g) is distilled off under water jet vacuum up to an internal temperature of from 150 - l70C. The residue is sub-mitted to a high vacuum distillation. 51 ~ of 2-methyl-2,S-dioxo-1,2-oxa~phospholane (boiling point at 0.6 mm Hg: 158C) are obtained, corresponding to 76.4 ~ of the theoretical yield.
E X A M P ~ E 8:
2,~-dimethyl-2,5-dioxo-1,2-o~phospholane based on methacrylic acid and 3-hydroxypropyl-met}lyl-phosphinic acid A mixture of 43 g (0.5 mole) of methacrylic acid and 69 g 1Q (0.5 mole) of 3-hydroxypropyl-methyl-phosphinic acid is added to 58.5 g ~0.5 mole) of methyldichloro-phosphine at 50 - 60C, while hydrogen chlor.ide is discharged. Subse~uently heating takeq place under water jet vacuum to an internA1 temperature of up to 150C. The residue is distilled under reduced pressure.
35 g of 2-methyl-2-oxo-1,2-oxa-phospholane (boiling point at 1.5 mm Hg: 120 - 130C) and 55 g of 2,4-dimethyl-2,5-dioxo-1,2-oxa-phospholane (boiling point at 0.7 ~m Hg: 150 - 155C) are ob-tained. The yield in 2,4-dimethyl-2,5-d-oxo-~,2-oxa-phospholane rcpresents 71 % of the theoretical yield.
~ X ~ M P L ~ 9 __ , 2-methyl-2,5 _ oxo-1,2-oxa~phos~h~lane based on acrylic acld and 8-h~oxybuty~-ic ~lcid A mixture of 52 g (0.5 mole) of 3-hydroxy-buty.ric acid and 36 g (0.5 mole) of acrylic acid is added dropwise to 58.5 g (0.5 mole) of methyl-dichloro-phosphine at 25 - 30C, while hydrogen chloride is discharged. Subsequently 65 g of butyro~
lactone are distilled off under water jet vacuum up to an in- .
ternal temperature of 180C.
29 The residue is submitted to a vacuum dist.illation. At a : . .

HOE 75/}~ 172 boiling point at 0.7 mm Hg: 173 - 175C distillatlon yields-53 g of 2~methyl-2,5-dioxo-1,2-oxa-phospholane, corresponding to a yield of 79 ~ of the theoretical yield.

'~

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a 2,5-dioxo-1,2-oxa-phospholane having the general formula I

(I) wherein R1 represents an alkyl group of a haloalkyl group having up to 18 carbon atoms, a cycloalkyl group having up to 8 carbon atoms, an alkenyl group having up to 8 carbon atoms, an aryl group having up to 14 carbon atoms, which may be substituted by lower alkyl groups having up to 4 carbon atoms, by lower alkoxy groups having up to 4 carbon atoms, halogen or by alkylated or dialkylated amino groups or an aralkyl group having up to 15 carbon atoms and which may be substituted in the same way as the aryl group, R2 represents an alkyl group having up to 4 carbon atoms or hydrogen; and R3 represents an alkyl radical having up to 4 carbon atoms, a phenyl radical or a phenyl radical which is substituted by halogen or by lower alkyl groups having up to 4 carbon atoms, a benzyl radical or hydrogen;
in which a dihalogenophosphine of the general formula II

(II) wherein R1 is as defined above and X represents chlorine or bromine is reacted with an equimolar quantity of an .alpha.,.beta.-unsat-urated acid of the formula III

(III) wherein R2 and R3 are as defined above and simultaneously with an equivalent quantity of a compound of the formula IV

R4 - OH (IV) wherein R4 represents hydrogen or an acyl radical having from 2 to 12 carbon atoms which may be substituted by a hydroxy group in the ?- or .delta.-position or which may be substituted once, twice or three times by halogen, or by a carboxyl group, or wherein R4 represents the radical -CO-COOH, an alkyl-sulfonyl radical, a phenyl-sulfonyl radical, a phenalkyl-sulfonyl radi-cal or an alkylphenyl-sulfonyl radical having up to 12 carbon atoms, or wherein R4 represents a radical of the formula IVa (IVa) wherein R5 represents an alkyl radical having up to 12 carbon atoms which may be substituted by halogen, a cycloalkyl radi-cal having up to 8 carbon atoms or an alkenyl radical having from 2 to 12 carbon atoms, and wherein R6 has the same mean-ing as specified for R5 or represents a carboxylic acid group having from 2 to 4 carbon atoms or HO(CH2)3 - or HO(CH2)n-, or with an equivalent quantity of a compound having the formula (V) wherein R5 and R6 are as defined above and wherein R7 has the meaning of R5 or represents a group of the formula IVa, or with an equivalent quantity of a mixture of the compounds having the formulae IV and V, and the reaction product is subsequently isolated.
2. A process as claimed in claim 1 in which the compound of the formula II is reacted with a mixture of the compounds of the formulae III and IV.
3. A process as claimed in claim 1 in which at least one of the radicals R2 or R3 represents a hydrogen atom.
4. A process as claimed in claim 1, claim 2 or claim 3 in which R1 represents an alkyl group having from 1 to 4 carbon atoms or a halogen-substituted alkyl group having from 1 to 4 carbon atoms, cyclohexyl, cyclopentyl, vinyl, allyl, phenyl or phenyl which is substituted by lower alkyl groups having up to 4 carbon atoms, lower alkoxy groups having up to 4 carbon atoms, halogen or by alkylated or dialkylated amino groups, or R1 represents benzyl.
5. A process as claimed in claim 1, claim 2 or claim 3 in which R2 represents methyl.
6. A process as claimed in claim 1, claim 2 or claim 3 in which R3 represents methyl.
7. A process as claimed in claim 1, claim 2 or claim 3 in which one of the radicals R2 and R3 represents hydrogen while the other radical represents hydrogen or methyl.
8. A process as claimed in claim 1, claim 2 or claim 3 in which the reaction temperature is in the range from -20° to +160°C.
9. A process as claimed in claim 1, claim 2 or claim 3 in which the reaction temperature is in the range of from 0°
to +100°C.
CA255,707A 1975-06-26 1976-06-25 Process for preparing 1,2-oxa-phospholanes Expired CA1079745A (en)

Applications Claiming Priority (1)

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DE2528420A DE2528420C2 (en) 1975-06-26 1975-06-26 Process for the preparation of 2,5-dioxo-1,2-oxa-phospholanes

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CA1079745A true CA1079745A (en) 1980-06-17

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JP (1) JPS523065A (en)
BE (1) BE843500A (en)
CA (1) CA1079745A (en)
CH (1) CH606057A5 (en)
DE (1) DE2528420C2 (en)
FR (1) FR2317307A1 (en)
GB (1) GB1538953A (en)
IT (1) IT1061436B (en)
NL (1) NL7606713A (en)

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DE19613061C2 (en) * 1996-04-01 1998-07-02 Clariant Gmbh Phosphorus-modified epoxy resins made from epoxy resins and phosphorus-containing compounds
EP0799846B1 (en) * 1996-04-01 2000-06-14 Clariant GmbH Phosphorus modified epoxy resin mixtures comprising epoxy resins, phosphorus-containing compounds and a curing agent
DE102006010362A1 (en) 2006-03-07 2007-09-13 Clariant International Limited Mixtures of mono-carboxyl-functionalized dialkylphosphinic acids, a process for their preparation and their use

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FR2317307A1 (en) 1977-02-04
GB1538953A (en) 1979-01-24
DE2528420C2 (en) 1984-03-08
NL7606713A (en) 1976-12-28
JPS523065A (en) 1977-01-11
IT1061436B (en) 1983-02-28
CH606057A5 (en) 1978-10-13
DE2528420A1 (en) 1977-01-13
FR2317307B1 (en) 1981-01-02
BE843500A (en) 1976-12-28

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