US3790648A - Process for the manufacture of benzylphosphonates - Google Patents

Process for the manufacture of benzylphosphonates Download PDF

Info

Publication number
US3790648A
US3790648A US00225615A US3790648DA US3790648A US 3790648 A US3790648 A US 3790648A US 00225615 A US00225615 A US 00225615A US 3790648D A US3790648D A US 3790648DA US 3790648 A US3790648 A US 3790648A
Authority
US
United States
Prior art keywords
formula
mol
phosphite
carbon atoms
tert
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00225615A
Other languages
English (en)
Inventor
A Schmidt
H Brunetti
K Schwarzenbach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis Corp
Original Assignee
Ciba Geigy Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ciba Geigy Corp filed Critical Ciba Geigy Corp
Application granted granted Critical
Publication of US3790648A publication Critical patent/US3790648A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4056—Esters of arylalkanephosphonic acids
    • 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
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids

Definitions

  • ABSTRACT OF THE DISCLOSURE Process for the manufacture of 4-hydroxybenzylphosphonic esters by reacting esters of phosphoric acid with 4-hydroxybenzylamines in the presence of a base.
  • the compounds manufactured according to the invention are used as stabilizers.
  • the present invention relates to a process for the manufacture of compounds of the Formula I I O R4 R:
  • R and R denote a straight-chain or branched alkyl group, a cycloalkyl group or an aralkyl group
  • R and R independently of one another denote a straightchain or branched alkyl group, a cycloalkyl group, an alkylthioalkyl group, an alkyloxalalkyl group, a halogenoalkyl group, an alkenyl group, the phenyl group or an alkylphenyl group, or together denote the groups characterized in that 1 mol of a compound of the Formula II I Ra B2 wherein R and R 'halve the abovementioned meaning and R and R independently of one another denote a straight-chain or branched alkyl group or together, and with inclusion of the nitrogen atom, denote a saturated "United States Patent ihce 3,790,648 Patented Feb.
  • dialkylamines split off during the reaction can easily be removed because of their volatility and can furthermore be trapped and reemployed for the manufacture of the starting products of the Formula II, which represents a further advantage in dustrially.
  • dialkyl phosphites used in the heterocyclic ring are reacted with one mol of a compound 7 of the Formula HI E O R4 (III) wherein R and B, have the aboven entioned meaning in the presence of a base.
  • R and R independently of one another denote a straight-chain or branched alkyl group with 1 to 8 carbon atoms or a cycloalkyl group with *6 to 8 carbon atoms and R and R independently of one another denote a straight-chain or branched alkyl group with 1-22 carbon atoms, a cycloalkyl group with 6-8 carbon atoms, the groups wherein the alkyl groups possess 1-18 carbon atoms, the phenyl group or an alkylphenyl group with 7-14 carbon atoms.
  • dialkyl In the preferred embodiment of the process according to the invention, compounds of the Formula II are used in which R and R independently of one another denote a straight-chain or branched alkyl group with 1 to 5 carbon atoms or together, with inclusion of the nitrogen atom, form a hydrogenated heterocyclic S-membered or 6-membered ring.
  • R denotes methyl or branched alkyl with 3-4 carbon atoms
  • R denotes branched alkyl with 3 or 4 carbon atoms
  • R and R denote straight-chain or branched alkyl groups with 1-18 carbon atoms.
  • Compounds ofthe Formula II in which R and R denote methyl, ethyl, propyl or isopropyl or together denote the radical of piperidine or morpholine are particularly preferentially employed for the manufacture of the compounds of the Formula I.
  • the process according to the invention can be carried out in the absence or in the presence of a solvent. Preferably, no solvent is used.
  • R R R R R and R represent alkyl groups, these can, within the framework of the limits which have been indicated, be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertbutyl, amyl, tert.arnyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octdecyl, eicosyl or docosyl.
  • These groups may also be alkyl substituents if R and R denote alkylphenyl.
  • R and R are halogenoalkyl groups, then these are preferably chloroalkyl groups with 1-18 carbon atoms, such as, for example, 2-chloroethyl.
  • R and R can also be cyclic alkyl groups with 6 to 8 carbon atoms. These can be, for example, cyclohexyl, cycloheptyl or cyclooctyl, and the preferred cyclic alkyl group is the l-methylcyclo- Preferred'temperature ranges are 60-120 C.
  • R and R are aralkyl groups, these can be groups with 7-12 carbon atoms, such as benzyl or phenylethyl. If R and R with inclusion of the nitrogen atom, form a heterocyclic S-membered or 6-membered ring, then this can be, for example, the radical of morpholine or piperidine.
  • R is alkylthioalkyl, it can be hexadecylthioethyl, dodecylthioethyl, hexylthioethyl, octadecylthiopropyl, dodecylthiopropyl or hexylthiopropyl.
  • R;., denotes alkyloxalalkyl this can be octadecyloxyethyl or dodecyloxyethyl.
  • R as alkenyl is, for example, allyl.
  • solvents are used in the process according tov the invention, then these can be aromatic hydrocarbons such as benzene or toluene, higher-boiling ethers, such as dioxane or ethylene glycol dimethyl ether, or aliphatic hydrocarbons or hydrocarbon mixtures, such as ligroin.
  • Bases in the process according to the invention are, for example, alkali amides such as LlNHg or NaNI-I alkali hydrides, such as NaH or Lil-I, alkali hydroxides, such as LiII-I, NaOH or KOH, alcoholates such as NaOCI-I NaOC H or Mg(OC H Alkali amides and alkali alcoholates are preferred.
  • Alkali compounds of the phosphites of the Formula 111 can also be employed as bases. Their manufacture is effected, for example, by adding an alkali metal such as sodium to a phosphite of the Formula III.
  • Examples of compounds of the Formula III are dimethyl phosphite, diethyl phosphite, dibutyl phosphite, dihexyl phosphite, di-Z-ethylhexyl phosphite,- dioctyl phospite, didodecyl phosphite, dihexadecyl phosphite, dioctadecyl phosphite, didocosyl phosphite, diphenyl phosphite I or di-p-octylphenyl phosphite.
  • the starting compounds of the Formula II canbe manufactured from the corresponding 2,6-dialkylphenol, formaldehyde and a secondary amine HNR R as described, for example, in Netherlands Pat. 6803498.
  • the reactants of the Formulae II and III are advantageously employed in molar ratios.
  • one of the two reactants can be used in an excess of up to 20%.
  • The-base is employed in amounts of 1-30 mol percent, preferably 5-10 mol percent, relative to one of the reactants ofcthe Formula II or III. 4
  • the temperature in the process according to the invention are not critical. They are only important with re- If, for example, the reaction is carried out at 100 C
  • the reaction according to the invention is preferably carried out under nitrogen or a noble gas, at normal pressure or reduced presusre, such as, for example, 10- mm. Hg.
  • the reaction according to the invention can be carried out, for example, by warming the Compounds 11 and III and the base, withoutsolvents, under reduced p ressure'until no further amine is evolved, or by adding the base 'to a solution of the Compound III and then adding the compound II, in the same solvent as the CompoundIH, at elevated temperature.
  • the compounds obtained in accordance with the process of the invention are outstandingly suitable for use as stabilizers against the thermo-oxidative and/or photo-induced degradation of monomeric and polymeric substances, especially for the stabilization of polypropylene, of polyethylene, of polyamides, of polyacetals or of copolymers of ethylene, propylene and a diene such as, for example, norbornadiene or dicyclopentadiene.
  • the diphenyl phosphite is replaced by an equimolecular amount of di-tert.octylphenyl phosphite and otherwise the same procedure is followed, 4- hydroxy-3,5-di-tert.butylbenzyl-phosphonic acid di-(tert. octylphenyl) ester is obtained in good yield, after distilling off the solvent, as a glass of a slight yellow color.
  • Process for the manufacture of compounds of the Formula I ii OR -onionlor which comprises reacting 1 mol of a compound of the Formula II HQ-QCm-N wherein R and R have the'abovementioned meaning and R and R independently of one another denote a straight-chain or branched alkyl group or together, and with inclusion of the nitrogen atom, denote a saturated heterocyclic ring, with one mol of a compound of the Formula III wherein R and R have the abovementioned meaning, in the presence of a base selected from alkali amides, alkali hydrides, alkali hydroxides, alkali alcoholates, and alkali compounds of the phosphites of the Formula III.
  • R and R denote a straight-chain or branched alkyl group or a cycloalkyl group and R and R inde: pendently of one another denote a straight-chain or branched alkyl group, a cycloalkyl group, an alkylthioalkyl group, an alkyloxalkyl group, an alkenyl group, the phenyl group or an alkylphenyl group or together denote the groups -omomor 3.
  • R and R independently of one another denote a straight-chain or branched alkyl group with 1 to 8 carbon atoms or a cycloalkyl group with 6 to 8 carbon atoms and R and R independently of one another denote a straight-chain or branched alkyl group with 1-22 carbon atoms,a cycloalkyl group with 6-8 carbon atoms, the --(CH -Sall yl or (CH 0alkyl groups, wherein the alkyl groups contain 1-18 carbon atoms, the phenyl group or an alkylphenyl group with 7-14 carbon atoms.
  • R and R independently of one another denote. alkylwith 1-5 carbon atoms or together and with inclusion of the nitrogen atom form a hydrogenated heterocyclic S-membered or fi-rnembered ring.
  • R denotes methyl or branched alkyl with 3-4 carbon atoms
  • R denotes branched alkyl with 3 or 4 carbon atoms
  • R and R denote straight-chain or branched alkyl groups with 1-18 carbon atoms.
  • R and R denote methyl, ethyl, propyl or isopropyl or together denote the radical of piperidine or morpholine.
  • R and R denote methyl, ethyl, propyl or isopropyl or together denote the radical of piperidine.

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)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US00225615A 1971-02-17 1972-02-11 Process for the manufacture of benzylphosphonates Expired - Lifetime US3790648A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH231571A CH542248A (de) 1971-02-17 1971-02-17 Verfahren zur Herstellung von Benzylphosphonaten

Publications (1)

Publication Number Publication Date
US3790648A true US3790648A (en) 1974-02-05

Family

ID=4230916

Family Applications (1)

Application Number Title Priority Date Filing Date
US00225615A Expired - Lifetime US3790648A (en) 1971-02-17 1972-02-11 Process for the manufacture of benzylphosphonates

Country Status (11)

Country Link
US (1) US3790648A (fr)
AT (1) AT309466B (fr)
BE (1) BE779422A (fr)
CA (1) CA926871A (fr)
CH (1) CH542248A (fr)
DE (1) DE2203837C3 (fr)
FR (1) FR2125515B1 (fr)
GB (1) GB1365622A (fr)
IT (1) IT950550B (fr)
NL (1) NL7202041A (fr)
SU (1) SU509240A3 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962376A (en) * 1973-09-25 1976-06-08 Ciba-Geigy Corporation 2,4,6-Trialkyl-3-hydroxyphenylalkane phosphonates and phosphinates
US3962377A (en) * 1973-09-25 1976-06-08 Ciba-Geigy Corporation 2,3,5-Trialkyl-4-hydroxybenzylphosphonates and phosphinates
US4008199A (en) * 1975-06-09 1977-02-15 Celanese Corporation Heat stabilized polyalkylene terephthalate resin composition
US4093588A (en) * 1974-10-07 1978-06-06 Ciba-Geigy Corporation Hindered phenolic cyclic phosphonates and stabilized compositions
US4210577A (en) * 1976-12-24 1980-07-01 Argus Chemical Corporation Stabilizers for synthetic polymers comprising 2,2,6,6-tetramethyl-4-piperidyl carboxylic acid ester, phosphonic acid ester and phenol
US4263232A (en) * 1979-07-09 1981-04-21 Ciba-Geigy Corporation Process for the manufacture of selected phosphonates
US5157141A (en) * 1989-11-29 1992-10-20 Ciba-Geigy Corporation Process for the preparation of hydroxybenzylphosphonates
US5171873A (en) * 1991-04-05 1992-12-15 Ciba-Geigy Corporation Process for the preparation of sterically hindered hydroxybenzylphosphonates
US5258540A (en) * 1989-11-29 1993-11-02 Ciba-Geigy Corporation Cyclohexyl substituted hydroxybenyzlphosphonates
EP0690064A1 (fr) 1994-06-28 1996-01-03 Ciba-Geigy Ag Procédé de préparation d'hydroxybenzylphosphonates à empêchement stérique
EP0816354A1 (fr) * 1996-06-25 1998-01-07 Bayer Ag Procédé pour la préparation et stabilisation de carbonates cycliques à six chainons
US5756596A (en) * 1993-12-16 1998-05-26 Ciba Specialty Chemicals Corporation Increasing the molecular weight of polyamides
WO2003026632A3 (fr) * 2001-09-26 2003-08-21 Theravance Inc Composes phenoliques substitues utiles pour l'anesthesie et la sedation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4128509A1 (de) * 1991-08-28 1993-03-04 Basf Ag Thermooxidationsbestaendige thermoplastische formmassen
DE4131951A1 (de) * 1991-09-25 1993-04-08 Boehme Chem Fab Kg Wasserloesliche bzw. dispergierbare mittel zur stabilisierung thermooxidativ labiler verbindungen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1917512A1 (de) * 1969-04-05 1970-10-15 Advance Prod Gmbh phosphonessigsaeureester

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962376A (en) * 1973-09-25 1976-06-08 Ciba-Geigy Corporation 2,4,6-Trialkyl-3-hydroxyphenylalkane phosphonates and phosphinates
US3962377A (en) * 1973-09-25 1976-06-08 Ciba-Geigy Corporation 2,3,5-Trialkyl-4-hydroxybenzylphosphonates and phosphinates
US4093588A (en) * 1974-10-07 1978-06-06 Ciba-Geigy Corporation Hindered phenolic cyclic phosphonates and stabilized compositions
US4008199A (en) * 1975-06-09 1977-02-15 Celanese Corporation Heat stabilized polyalkylene terephthalate resin composition
US4210577A (en) * 1976-12-24 1980-07-01 Argus Chemical Corporation Stabilizers for synthetic polymers comprising 2,2,6,6-tetramethyl-4-piperidyl carboxylic acid ester, phosphonic acid ester and phenol
US4222931A (en) * 1976-12-24 1980-09-16 Argus Chemical Corporation Stabilizers for synthetic polymers comprising 2,2,6,6-tetramethyl-4-piperidyl ether alcohol or ether, phosphonic acid ester and phenolic antioxidant
US4263232A (en) * 1979-07-09 1981-04-21 Ciba-Geigy Corporation Process for the manufacture of selected phosphonates
EP0434606B1 (fr) * 1989-11-29 1995-08-16 Ciba-Geigy Ag Hydroxybenzylphosphonates et leur procédé de préparation
US5258540A (en) * 1989-11-29 1993-11-02 Ciba-Geigy Corporation Cyclohexyl substituted hydroxybenyzlphosphonates
US5157141A (en) * 1989-11-29 1992-10-20 Ciba-Geigy Corporation Process for the preparation of hydroxybenzylphosphonates
US5171873A (en) * 1991-04-05 1992-12-15 Ciba-Geigy Corporation Process for the preparation of sterically hindered hydroxybenzylphosphonates
US5756596A (en) * 1993-12-16 1998-05-26 Ciba Specialty Chemicals Corporation Increasing the molecular weight of polyamides
EP0690064A1 (fr) 1994-06-28 1996-01-03 Ciba-Geigy Ag Procédé de préparation d'hydroxybenzylphosphonates à empêchement stérique
US5618963A (en) * 1994-06-28 1997-04-08 Ciba-Geigy Corporation Process for the preparation of sterically hindered hydroxybenzylphosphonates
EP0816354A1 (fr) * 1996-06-25 1998-01-07 Bayer Ag Procédé pour la préparation et stabilisation de carbonates cycliques à six chainons
US5861107A (en) * 1996-06-25 1999-01-19 Bayer Aktiengesellschaft Process for the preparation of aliphatic carbonates having a six-membered ring
WO2003026632A3 (fr) * 2001-09-26 2003-08-21 Theravance Inc Composes phenoliques substitues utiles pour l'anesthesie et la sedation
US6815555B2 (en) 2001-09-26 2004-11-09 Theravance, Inc. Substituted phenol compounds useful for anesthesia and sedation
US20050032753A1 (en) * 2001-09-26 2005-02-10 Jenkins Thomas E. Substituted phenol compounds useful for anesthesia and sedation
US7226946B2 (en) 2001-09-26 2007-06-05 Theravance, Inc. Substituted phenol compounds useful for anesthesia and sedation

Also Published As

Publication number Publication date
BE779422A (fr) 1972-08-16
AT309466B (de) 1973-08-27
NL7202041A (fr) 1972-08-21
FR2125515B1 (fr) 1974-09-13
DE2203837A1 (de) 1972-08-31
DE2203837C3 (de) 1981-07-23
CH542248A (de) 1973-09-30
CA926871A (en) 1973-05-22
GB1365622A (en) 1974-09-04
FR2125515A1 (fr) 1972-09-29
IT950550B (it) 1973-06-20
DE2203837B2 (de) 1980-06-26
SU509240A3 (ru) 1976-03-30

Similar Documents

Publication Publication Date Title
US3790648A (en) Process for the manufacture of benzylphosphonates
US2578652A (en) Addition product of diester of dithiophosphoric acid and maleic acid and its esters, and method of preparation
US3270091A (en) Hydroxyphenylalkane phosphonic acids and esters thereof
US4382042A (en) Method of preparing oligomeric phosphate esters
US4290976A (en) Process for the preparation of phenol-free phosphites
US3280070A (en) Stabilization of unstable organic material with phosphonates, phosphates and/or thiodipropionates
US2754320A (en) Production of diesterified phosphono derivatives of monofunctional compounds
JP2924357B2 (ja) 亜リン酸エステル化合物、その製法および用途
US3787540A (en) Benzylation of dialkyl phosphites with dithiourethanes
US3629189A (en) Enhancement of resistance of olefin polymers to copper-catalyzed oxidative degradation
US3155703A (en) Bicyclic phosphites and phosphates
US3821334A (en) Process for the manufacture of p-hydroxybenzyl compounds
US4046774A (en) Process for N-phosphorylation of heterocyclic amines
US3907517A (en) Normally liquid hydrocarbon compositions containing amidatriazales
US2535173A (en) 3-phosphonopropane-1, 1-dicarboxylic acid esters and method of preparation
US3784650A (en) 3,5-dialkyl-4-hydroxybenzyl mercapto (acetic acid ester)containing phosphites
US2305529A (en) Cyanoethylated aryl acetonitreles
US4056571A (en) Process for the preparation of tertiary phosphine oxides
EP0098109B1 (fr) Composés contenant du phosphore, leur préparation et leur utilisation comme antioxidants
DE3928291A1 (de) Phosphorigsaeure-arylester-amid-halogenide, phosphonigsaeurearylester-amide, verfahren zu ihrer herstellung und deren verwendung zur stabilisierung von kunststoffen
US4107137A (en) Phenolic antioxidants for synthetic polymers
US2973380A (en) Phosphonates
DE2612131C3 (de) Verfahren zur Herstellung von phenolfreien Dialkylpentaerythritdiphosphiten
US4263232A (en) Process for the manufacture of selected phosphonates
US2793225A (en) Process for preparing phosphonic acid esters