US3787540A - Benzylation of dialkyl phosphites with dithiourethanes - Google Patents
Benzylation of dialkyl phosphites with dithiourethanes Download PDFInfo
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- US3787540A US3787540A US00250539A US3787540DA US3787540A US 3787540 A US3787540 A US 3787540A US 00250539 A US00250539 A US 00250539A US 3787540D A US3787540D A US 3787540DA US 3787540 A US3787540 A US 3787540A
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- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 title description 10
- 238000005574 benzylation reaction Methods 0.000 title 1
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 150000003009 phosphonic acids Chemical class 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract 2
- 238000000034 method Methods 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 125000000217 alkyl group Chemical group 0.000 description 25
- 125000004432 carbon atom Chemical group C* 0.000 description 25
- -1 benzyl halides Chemical class 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002585 base Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 150000001350 alkyl halides Chemical class 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 6
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZHBRSHSRMYZHLS-UHFFFAOYSA-N (4-hydroxyphenyl)methylphosphonic acid Chemical class OC1=CC=C(CP(O)(O)=O)C=C1 ZHBRSHSRMYZHLS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical group CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 150000003938 benzyl alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- BAKDLAFAVHBXHW-UHFFFAOYSA-N dioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP([O-])OCCCCCCCCCCCCCCCCCC BAKDLAFAVHBXHW-UHFFFAOYSA-N 0.000 description 2
- 229950004394 ditiocarb Drugs 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NBGHWWFWFLNKMX-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2,6-di(propan-2-yl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)C)=C(O)C(C(C)C)=C1 NBGHWWFWFLNKMX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CJXGDWDDLMZNBC-UHFFFAOYSA-N P(O)(O)=O.P(O)(O)O Chemical compound P(O)(O)=O.P(O)(O)O CJXGDWDDLMZNBC-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([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 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000002511 behenyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([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 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 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 description 1
- 239000012074 organic phase Substances 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl 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])C([H])([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 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([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 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 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
- C07F9/38—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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
- C09K15/322—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus
- C09K15/324—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus containing phosphorus and sulfur
Definitions
- Esters of p-hydroxybenzylphosphonic acids are prepared by reacting p-hydroxybenzyldithiourethans with esters of phosphonic acids in the presence of a base. The esters of p-hydroxybenzylphosphonic acids are stabilizers for polymers.
- the present invention relates to a process for the manufacture of compounds of the Formula I wherein R and R independently of one another denote a straight-chain or branched alkyl group, a cycloalkyl group or an aralkyl group, and R and R independently of one another denote a straight-chain or branched alkyl group, a cycloalkyl group, an alkylthioalkyl group, an alkyloxalkyl group, a halogenoalkyl group, an alkenyl group, the phenyl group or an alkylphenyl group or together denote the groups CH CH or characterized in that 1 mol of a compound of the Formula II wherein R and R have the abovementioned meaning and R and R independently of one another denote a straightchain or branched alkyl group or together, with inclusion of the nitrogen atom, denote a saturated heterocyclic ring, is reacted with one'mol of a compound of the Formula III wherein R and R have the abovement
- the process according to the invention avoids the formation of alkyl halide during the reaction, and this substantially facilitates the purification of the end product. Furthermore, the process according to the invention is economically advantageous because the dialkyl phosphite used, of the Formula III, is practically 3,787,540 Patented Jan. 22, 1974 completely incorporated into the end product of the Formula I, whilst according to the previously known process a part of the trialkyl phosphite is lost in the form of the alkyl halide.
- the relatively low reaction temperatures and the short reaction times which represses the undesired formation of colored by-products.
- the N,N-dialkyldithiocarbamates which are split off during the reaction can easily be separated off in the form of their watersoluble salts. These splitting products can therefore be isolated and again employed for the manufacture of the starting products of the Formula II, and this represents a further technical advantage.
- the dialkyl phosphites used in the process according to the invention are substantially less volatile when compared to the corresponding trialkyl phosphites hitherto used, and therefore cause distinctly less objectionable odor during the reaction.
- 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.
- compounds of the Formula I in which R denotes methyl or branched alkyl with 3-4 carbon atoms, R denotes branched alkyl with 3 or 4 carbon atoms and R and R denote straight-chain or branched alkyl groups with 1-22 carbon atoms, propenyl, a C H S--alkyl group with 14-20 carbon atoms or phenyl, are manufactured according to the invention.
- R and R denote methyl, ethyl or propyl or together denote the radical of piperidine are employed for the manufacture of the compounds of the Formula L
- R R R R R and R represent alkyl groups, these can, within the framework of the indicated limits, be methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, tert.
- R and R can also be cyclic alkyl groups with 6 to 8 carbon atoms.
- R and R as aralkyl groups can, for example, denote benzyl or a-phenyl-ethyl. If R and R with inclusion of the nitrogen atom, form a heterocyclic S-membered or 6-membered ring, this can be, for example, the radical of morpholine or piperidine.
- R is alkylthioalkyl, it can be hexadecylthioethyl, dodecylthioethyl, octylthioethyl, hexylthioethyl, ethylthioethyl, octadecylthiopropyl, dodecylthiopropyl or hexylthio propyl.
- R denotes alkyloxyalkyl it can be dodecyloxyethyl or octadecyloxyethyl.
- Rla as alkenyl is, for example, allyl.
- the solvents used in the process according to the invention are, for example, aromatic hydrocarbons such as benzene or toluene, higher-boiling ethers, such as dioxane or ethylene glycol dimethyl ether, aliphatic hydrocarbons, or hydrocarbon mixtures such as ligroin. Preferred solvents are ligroin and toluene.
- Bases used in the process according to the invention are, for example, alkali amides, such as LiNH- and NaNH and alcoholates such as NaOCH NaOC H and Mg(OC- H Alkali amides are preferred.
- Examples of compounds of the Formula III are dimethyl, diethyl, dibutyl, dihexyl, di-Z-ethylhexyl, dioctyl, didodecyl, dihexadecyl, dioctadecyl, didocosyl, diphenyl or di-p-octylphenyl phosphite.
- the starting compounds of the Formula II can be manufactured from the corresponding 2,6-dialkylphenol, formaldehyde, carbon disulphide and a secondary amine, as described, for example, in US. Pat. 2,757,174.
- the reactants of the Formulas l1 and III are advantageously employed in molar ratios. If desired, one of the two reactants can be used in up to 20% excess.
- the base is employed in molar amounts relative to the Compound III.
- the temperatures in the process according to the invention are not critical. They are only important for the speed at which the reaction takes place. If, for example, the process is carried out at 70 C., the reaction time is between 60 minutes and a few hours. Preferred temperature ranges are 40-100 C.
- the reaction according to the invention is preferably carried out whilst passing nitrogen or a noble gas through the mixture.
- the reaction according to the invention can for example be carried out by adding the base to a solution of the Compound III and then adding the Compound 11 in the same solvent as the Compound III, 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 light-induced degradation of monomeric and polymeric substances, especially for the stabilisation of polypropylene, polyethylene, polyamides, polyurethanes, polyacetals or copolymers of ethylene, propylene and a diene such as, for example, norbornadiene or dicyclopentadiene.
- tertJoutyl 13.8 g. (0.1 mol) of diethyl phosphite are dissolved in 50 ml. of ligroin and 3.9 g. (0.1 mol) of sodium amide are added.
- 36.8 g. (0.1 mol) of N,N-diethyl-dithiocarbamic acid 3,S-ditert.butyl-4-hydroxybenzyl ester, dissolved in ml. of hot ligroin, are added dropwise at 60 C. The mixture is kept for 3 hours at 70 C. and is then cooled to room temperature, and 200 ml. of toluene are added. The toluene solution is repeatedly Washed with water and evaporated. The residue is recrystallized from ligroin. 27 g. (75%) of 4-hydroxy-3,S-ditert.butylbenzylphosphonic acid dialkyl ester of melting point 122 C. ar thus obtained.
- the diethyl phosphite is replaced by an equimolecular amount of one of the dialkyl phosphites of the Table 1 below and otherwise the same procedure is followed, the 4-hydroxy-3,6-ditert.butylbenzylphosphonic acid dialkyl esters having the indicated physical data are obtained.
- EXAMPLE 4 tert.butyl i /P ⁇ 110- CH2-S-CN ⁇ 0 H C2110 tert.butyl tert.butyl 0/0 0:11. 130- CHr-P ⁇ OCs a tert.butyl
- the procedure of Example 1 is repeated, the diethyl phosphite being replaced by an equimolecular amount of diphenyl phosphite or di- (p-tert.octylphenyl)-phosphite.
- R and R independently of one another are a straight-chain or branched alkyl group with l to 8 carbon atoms or a cycloalkyl group with 6 to 8 carbon atoms and R and R independently of one another are a straight-chain or branched alkyl group with 1-22 carbon atoms, the Sa1kyl 01' z -Oalkyl groups, wherein the alkyl groups possess 1-8 carbon atoms, an alkenyl group with 3 or 4 carbon atoms or the phenyl group.
- R and R independently of one another are 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 are' a straight-chain or branched alkyl group with 1-22 carbon atoms or the S-alkyl O1 -O-alkyl groups, wherein the alkyl groups possess 1-8 carbon atoms.
- R and R independently of one another are alkyl with 1-5 carbon atoms or together, with inclusion of the nitrogen atom, form a hydrogenated heterocyclic S-mernbered or 6- membered ring.
- R is methyl or branched alkyl with 3-4 carbon atoms
- R is branched alkyl with 3 or 4 carbon atoms and R and R; are straightchain or branched alkyl groups with 1-22 carbon atoms, propenyl, a C H S-a1kyl group with 14-20 carbon atoms or phenyl.
- R and R are methyl, ethyl, propyl, isopropyl or together are the radical of piperidine.
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- Organic Chemistry (AREA)
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH697271A CH560227A5 (de) | 1971-05-12 | 1971-05-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3787540A true US3787540A (en) | 1974-01-22 |
Family
ID=4317922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00250539A Expired - Lifetime US3787540A (en) | 1971-05-12 | 1972-05-05 | Benzylation of dialkyl phosphites with dithiourethanes |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3787540A (de) |
| CH (1) | CH560227A5 (de) |
| DE (1) | DE2222708A1 (de) |
| ES (1) | ES402585A1 (de) |
| FR (1) | FR2137734B1 (de) |
| GB (1) | GB1362765A (de) |
| IT (1) | IT955415B (de) |
| NL (1) | NL7206341A (de) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4093588A (en) * | 1974-10-07 | 1978-06-06 | Ciba-Geigy Corporation | Hindered phenolic cyclic phosphonates and stabilized compositions |
| 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 |
| US5618963A (en) * | 1994-06-28 | 1997-04-08 | Ciba-Geigy Corporation | Process for the preparation of sterically hindered hydroxybenzylphosphonates |
| WO1999018112A1 (fr) * | 1997-10-06 | 1999-04-15 | Idemitsu Kosan Co., Ltd. | Composes organophosphoreux renfermant du soufre |
-
1971
- 1971-05-12 CH CH697271A patent/CH560227A5/xx not_active IP Right Cessation
-
1972
- 1972-05-05 US US00250539A patent/US3787540A/en not_active Expired - Lifetime
- 1972-05-09 DE DE19722222708 patent/DE2222708A1/de active Pending
- 1972-05-10 IT IT24200/72A patent/IT955415B/it active
- 1972-05-10 FR FR7216726A patent/FR2137734B1/fr not_active Expired
- 1972-05-10 GB GB2194872A patent/GB1362765A/en not_active Expired
- 1972-05-10 ES ES402585A patent/ES402585A1/es not_active Expired
- 1972-05-10 NL NL7206341A patent/NL7206341A/xx unknown
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4093588A (en) * | 1974-10-07 | 1978-06-06 | Ciba-Geigy Corporation | Hindered phenolic cyclic phosphonates and stabilized compositions |
| US5157141A (en) * | 1989-11-29 | 1992-10-20 | Ciba-Geigy Corporation | Process for the preparation of hydroxybenzylphosphonates |
| US5258540A (en) * | 1989-11-29 | 1993-11-02 | Ciba-Geigy Corporation | Cyclohexyl substituted hydroxybenyzlphosphonates |
| US5171873A (en) * | 1991-04-05 | 1992-12-15 | Ciba-Geigy Corporation | Process for the preparation of sterically hindered hydroxybenzylphosphonates |
| US5618963A (en) * | 1994-06-28 | 1997-04-08 | Ciba-Geigy Corporation | Process for the preparation of sterically hindered hydroxybenzylphosphonates |
| WO1999018112A1 (fr) * | 1997-10-06 | 1999-04-15 | Idemitsu Kosan Co., Ltd. | Composes organophosphoreux renfermant du soufre |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2137734A1 (de) | 1972-12-29 |
| GB1362765A (en) | 1974-08-07 |
| FR2137734B1 (de) | 1974-09-27 |
| IT955415B (it) | 1973-09-29 |
| DE2222708A1 (de) | 1972-11-23 |
| ES402585A1 (es) | 1975-03-16 |
| NL7206341A (de) | 1972-11-14 |
| CH560227A5 (de) | 1975-03-27 |
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