DK152726B - Fremgangsmaade til fremstilling af monoacetaler af aromatiske 1,2-diketoner - Google Patents
Fremgangsmaade til fremstilling af monoacetaler af aromatiske 1,2-diketoner Download PDFInfo
- Publication number
- DK152726B DK152726B DK416373AA DK416373A DK152726B DK 152726 B DK152726 B DK 152726B DK 416373A A DK416373A A DK 416373AA DK 416373 A DK416373 A DK 416373A DK 152726 B DK152726 B DK 152726B
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- Prior art keywords
- benzil
- atoms
- acetal
- aromatic
- alkyl
- Prior art date
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- 238000000034 method Methods 0.000 title description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 150000003138 primary alcohols Chemical class 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 20
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
- 150000001241 acetals Chemical class 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 4
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229960005323 phenoxyethanol Drugs 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YBHCENFWWFXYNH-UHFFFAOYSA-N 2,2-bis(2-butoxyethoxy)-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCOCCCC)(OCCOCCCC)C(=O)C1=CC=CC=C1 YBHCENFWWFXYNH-UHFFFAOYSA-N 0.000 description 2
- PGSAGOTVDYJQMN-UHFFFAOYSA-N 2,2-bis(2-phenoxyethoxy)-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1OCCOC(C=1C=CC=CC=1)(OCCOC=1C=CC=CC=1)C(=O)C1=CC=CC=C1 PGSAGOTVDYJQMN-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- -1 benzyl dimethyl acetal Chemical compound 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 1
- QGVJJXJRGYQAST-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)ethane-1,2-dione Chemical compound CC1=CC=CC=C1C(=O)C(=O)C1=CC=CC=C1C QGVJJXJRGYQAST-UHFFFAOYSA-N 0.000 description 1
- XDYSRWNBAYVIGW-UHFFFAOYSA-N 1,2-bis(3-bromophenyl)ethane-1,2-dione Chemical compound BrC1=CC=CC(C(=O)C(=O)C=2C=C(Br)C=CC=2)=C1 XDYSRWNBAYVIGW-UHFFFAOYSA-N 0.000 description 1
- BCWCEHMHCDCJAD-UHFFFAOYSA-N 1,2-bis(4-methylphenyl)ethane-1,2-dione Chemical compound C1=CC(C)=CC=C1C(=O)C(=O)C1=CC=C(C)C=C1 BCWCEHMHCDCJAD-UHFFFAOYSA-N 0.000 description 1
- LVSZQGATCLRLCP-UHFFFAOYSA-N 1,2-bis(4-propan-2-ylphenyl)ethane-1,2-dione Chemical compound C1=CC(C(C)C)=CC=C1C(=O)C(=O)C1=CC=C(C(C)C)C=C1 LVSZQGATCLRLCP-UHFFFAOYSA-N 0.000 description 1
- RURQFXYDNRAWNW-UHFFFAOYSA-N 1,2-diphenyl-2,2-bis(2-phenylethoxy)ethanone Chemical compound C=1C=CC=CC=1CCOC(C=1C=CC=CC=1)(OCCC=1C=CC=CC=1)C(=O)C1=CC=CC=C1 RURQFXYDNRAWNW-UHFFFAOYSA-N 0.000 description 1
- GLDXCBVHFHZTKV-UHFFFAOYSA-N 1-(3-methoxyphenyl)-2-phenylethane-1,2-dione Chemical compound COC1=CC=CC(C(=O)C(=O)C=2C=CC=CC=2)=C1 GLDXCBVHFHZTKV-UHFFFAOYSA-N 0.000 description 1
- BHVXATXMHZWDFK-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-(4-phenylphenyl)ethane-1,2-dione Chemical compound C1=CC(Cl)=CC=C1C(=O)C(=O)C1=CC=C(C=2C=CC=CC=2)C=C1 BHVXATXMHZWDFK-UHFFFAOYSA-N 0.000 description 1
- QKFICTUTRIMBEX-UHFFFAOYSA-N 1-(4-methylphenyl)-2-phenylethane-1,2-dione Chemical compound C1=CC(C)=CC=C1C(=O)C(=O)C1=CC=CC=C1 QKFICTUTRIMBEX-UHFFFAOYSA-N 0.000 description 1
- IMHIDILLANKTRJ-UHFFFAOYSA-N 1-phenyl-2-(2,4,6-trimethylphenyl)ethane-1,2-dione Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C(=O)C1=CC=CC=C1 IMHIDILLANKTRJ-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- WBBPRCNXBQTYLF-UHFFFAOYSA-N 2-methylthioethanol Chemical compound CSCCO WBBPRCNXBQTYLF-UHFFFAOYSA-N 0.000 description 1
- KWWZHCSQVRVQGF-UHFFFAOYSA-N 2-phenylsulfanylethanol Chemical compound OCCSC1=CC=CC=C1 KWWZHCSQVRVQGF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- WVHBHPATSLQXGC-UHFFFAOYSA-N benzene;ethanol Chemical compound CCO.C1=CC=CC=C1 WVHBHPATSLQXGC-UHFFFAOYSA-N 0.000 description 1
- VFGRALUHHHDIQI-UHFFFAOYSA-N butyl 2-hydroxyacetate Chemical compound CCCCOC(=O)CO VFGRALUHHHDIQI-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Lubricants (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
DK 152726B
Den foreliggende opfindelse angår en særlig fremgangsmåde til fremstilling af monoacetaler af aromatiske 1,2-diketo-ner og med den almene formel
Ar1-C=0 2 1 1
Ar -C(OCH2R )2 (I) 5 hvori R^ betyder hydrogen, alkyl med 1-5 C-atomer, alkenyl med 2 eller 3 C-atomer, aralkyl med 7-9 C-atomer, aralkenyl
med 8 eller 9 C-atomer eller en gruppe -(CEU) -X, hvor X
2 2 3 3 ^ n betyder halogen, -OR , -SR , -OAr , -SAr , 0 0 u o 11 9 2 -O-C-R eller -C-OR , n et helt tal fra 1-3, R er alkyl 12 3 10 med 1-4 C-atomer, og Ar , Ar og Ar hver for sig betyder en usubstitueret eller med halogen, alkyl eller -O-alkyl med 1-4 C-atomer eller phenyl højst trisubstitueret phenylgruppe.
Det er kendt at fremstille dimethylacetalet af benzil ved omsætning af benzil med et stort overskud af bariumoxid og 15 methyliodid i dimethylformamid (Chem.Berichte 9£, 2258 (1961)). Man får derved efter fraskillelse af benzilsyremethylester, der dannes som biprodukt, og efter flere rensningsoperationer ben-zildimethylacetalet i 40%'s udbytte. Denne fremgangsmåde er uøkonomisk til teknisk fremstilling, da den fordrer dyre rea-20 genser og giver lave udbytter. Den er heller ikke teknisk anvendelig til fremstilling af de højere homologe. Fra Liebigs Analen der Chemie, bd. 485, side 283-295, er det endvidere kendt at fremstille dialkylacetaler ud fra monoketoner og dial-kylsulfiter i nærværelse af katalytiske mængder mineralsyre.
25 Når der ved denne kendte fremgangsmåde anvendes benzil som udgangsketon, opnås imidlertid kun et meget urent råprodukt i ringe udbytte, jfr. Chem. Ber. 9j[ (1962) , 2261.
Man har nu fundet en fremgangsmåde, der kan anvendes generelt til fremstilling af monoacetaler af aromatiske 1,2-diketoner 30 med formlen I på enkel måde med højt udbytte og renhed. Fremgangsmåden ifølge opfindelsen er ejendommelig ved, at man om-
DK 152726 B
2 sætter en aromatisk lf2-diketon med formlen
0 O
Ar^C-C-Ar2 (II) 1 2 hvori Ar og Ar har ovennævnte betydninger, med thionyl-chlorid og en primær alkohol med formlen R^CH^OH, hvori R^ 5 har ovennævnte betydning, idet man gennemfører omsætningen først ved 0 til 20°C og derefter ved 20 til 120°C, fortrinsvis 40 til 100°C.
Eksempler på aromatiske 1,2-diketoner med formlen (II), som kan anvendes ved fremgangsmåden ifølge opfindelsen, er benzil 10 og substituerede benziler som f.eks. 4,4'-dimethylbenzil, 4,4'-diisopropylbenzil, 4,41-diphenylbenzil, 2,21-dimethoxy-benzil, 4-methylbenzil, 3-methoxybenzil, 2,2'-dimethylbenzil, 4-chlor-4'-phenylbenzil, 4,4'-dichlorbenzil, 3,3'-dibromben-zil, 2,4,2',i'-tetramethylbenzil, 2,4,6-trimethylbenzil og 15 2,4-dichlor-41-methylbenzil. Fremstillingen af disse benzil- derivater er beskrevet i litteraturen og udføres f.eks. ved oxidation af de tilsvarende benzoiner.
Som eksempler på primære alkoholer R^Cf^OH, som anvendes ved fremgangsmåden ifølge opfindelsen, kan anføres methanol, 20 ethanol, propanol, butanol, hexanol, allylalkohol, β-phenyl-ethylalkohol, γ-phenylallylalkohol, 2-chlorethanol, 2-methoxy-ethanol, 2-phenoxyethanol, 2-methylthioethanol, 2-phenylthio-ethanol, 2-acetoxyethanol, hydracrylsyremethylester eller glycolsyrebutylester.
25 Omsætningen af diketonen med en blanding af thionylchlorid og alkohol udføres i et første trin under afkøling til 0 til 20°C, hvorved sulfitet dannes. Derpå foretages opvarmning til 20-120°C, fortrinsvis 40-100°C, hvorved den egentlige acetalisering foregår.
30 Isoleringen af benzil-monoacetalerne fra reaktionsblandingerne udføres efter kendte fremgangsmåder, f.eks. ved inddamp-ning af opløsningen, ved fortynding med vand eller ved afkø-
DK 152726 B
3 ling. Man får derved udbytter på over 80% af råt monoacetal, som efter behov kan renses ved omkrystallisering, destillation eller andre kendte rensningsmetoder.
De ved fremgangsmåden ifølge opfindelsen fremstillede benzil-5 monoacetaler kan anvendes som sensibilisatorer til fotopolymerisation af polymerisationsdygtige systemer, der indeholder umættede forbindelser, samt til fotokemisk tværbinding af lineære polymerisater.
Fremgangsmåden ifølge opfindelsen illustreres nærmere i de 10 nedenstående eksempler.
Eksempel 1.
Fremstilling af benzildimethylacetal 210,2 g benzil suspenderes i 238,0 g thionylchlorid. Denne suspension afkøles til 4°C, og 128,0 g methanol dryppes under 15 rolig omrøring til i løbet af 2 timer. Temperaturen holdes herunder mellem 2 og 7°C. Efter tildrypningen lader man reaktionsblandingen langsomt opvarme til stuetemperatur. Man får derved en klar, gul opløsning. Derpå opvarmer man i løbet af 30 minutter til 50°C, og der omrøres 1 time ved denne tempera-20 tur. Det overskydende dimethylsulfit afdestilleres i vakuum, den olieagtige remanens optages i 400 ml isopropanol, og til den klare opløsning sættes 25 g kaliumcarbonat og 7 ml tri-methylphosphit. Ved afkøling udskiller der sig et krystallinsk bundfald. Mellem 7 og 10°C tildryppes 350 ml vand, og reak-25 tionsblandingen udrøres derpå. Det krystallinske bundfald sugefiltreres, vaskes med isopropanol/vand i forholdet 1:1 og tørres ved 40° under vakuum.
Man får således benzildimethylacetal i form af hvide krystaller i et udbytte på 84% af det teoretiske.
4
DK 152726B
Eksempel 2-4,
Fremstilling af benzil-dialkylacetaler 21 g benzil suspenderes i 23,8 g thionylchlorid. Under afkøling til ca. 5°C tildryppes langsomt den i søjle 2 i tabel-5 len nedenfor angivne mængde alkanol. Efter fjernelse af køleapparaturet omrøres 4 timer ved stuetemperatur og yderligere 1 time ved 50°C. Den gule opløsning inddampes under vakuum, den olieagtige remanens opløses i 40 ml isopropanol, og opløsningen tilsættes 3 g kaliumcarbonat og 0,6 ml trimethyl-10 phosphit. Efter tilsætning af 30 ml vand udskiller der sig et krystallinsk bundfald af det i søjle 3 i tabellen nedenfor viste produkt, og bundfaldet filtreres fra og omkrystalliseres fra isopropanol. · · f---- i Eksempel Anvendt alkohol Produkt Smp./Kp.
I---—:--
15 ' 2 19 g ethanol benzen-diethylacetal smp. 61-62°C
3 24 g n-propanol benzen-di-n-propyl-
- acetal smp. 46-47°C
I Q
I 4 30 g n-butanol benzen-di-n-butyl- kp. 175 C/ ! acetal 0,5 mm Hg i_________
Eksempel 5.
Fremstilling af benzil-di-β-methoxyethyl-acetal 20 21,0 g benzil suspenderes i 23,8 g thionylchlorid, og der af køles til 0°C. Indenfor 30 minutter dryppes til denne suspension 30,4 g β-methoxyethanol, idet temperaturen ved køling holdes mellem 2 og 7°C. Reaktionsblandingen bringes indenfor 6 timer på stuetemperatur, hvorved der fås en klar opløsning.
25 Herpå opvarmes 1 time på 60°C. Påfølgende koncentreres den klare opløsning på en rotationsfordamper. Remanensen optages i 40 ml isopropanol og omsættes med 3 g kaliumcarbonat og 0,6 ml trimethylphosphit. Under køling tildryppes 35 ml vand,
DK 152726 B
5 hvorved hvide krystaller begynder at skille ud. Disse sugefiltreres fra og omkrystalliseres fra ethanol. Man får således benzen-di-p-methoxyethyl-acetal i form af hvide krystaller med et smeltepunkt på 67-69°C.
5 Eksempel 6.
Fremstilling af benzil-di-fi-chlorethyl-acetal
En suspension af 21,0 g benzil i 23,8 g thionylchlorid afkøles til 0°C. Mellem 0 og 5°C dryppes til denne suspension indenfor 30 minutter 35,3 g 2-chlorethanol. Reaktionsblandin-10 gen omrøres derpå 6 timer ved stuetemperatur og derefter 1 time ved 50-60°C. Efter koncentrering på en rotationsfordamper omsættes remanensen med 3 g kaliumcarbonat og 0,6 ml tri-methylphosphit og optages påfølgende i 40 ml isopropanol.
Ved tilsætning af vand dannes et krystallinsk bundfald. Dette 15 suqefiltreres fra og omkrystalliseres fra isopropanol. Man får således benzil-di-3-chlorethyl-acetal i form af hvide krystaller med et smeltepunkt på 58-59°C.
Eksempel 7.
Fremstilling af benzil-di-3-bromethyl-acetal 20 Til en suspension af 21,0 g benzil i 23,8 g thionylchlorid, som afkøles til 0°C, dryppes under køling indenfor 30 minutter 50,0 g 2-bromethanol. Efter tildrypningen omrører.man reaktionsblandingen i 8 timer ved stuetemperatur og .derpå 1 time ved 50-60°C. Herpå koncentreres under vakuum, og remanensen 25 opløses i 40 ml isopropanol og omsættes med 3,0 g kaliumcarbonat og 0,6 ml trimethylphosphit. Ved tilsætning af vand danner der sig et krystallinsk bundfald, som sugefiltreres fra og omkrystalliseres fra isopropanol. Man får således benzil-di-|3-bromethyl-acetal i form af hvide krystaller med et smel-30 tepunkt på 79-80°C.
DK 152726 B
6
Eksempel 8.
Fremstilling af benzil-di-(2-butoxyethyl)-acetal 21,0 g benzil (0,1 mol) suspenderes i 23,8 g (0,2 mol) thio-nylchlorid og afkøles til 0°C. I løbet af 30 minutter ind-5 dryppes der i denne suspension 48 g (0,4 mol) 3“butoxyethanol, idet temperaturen holdes mellem 2 og 7°C under afkøling. Reaktionsblandingen bringes i løbet af 6 timer på stuetemperatur, hvorved der fås en klar opløsning. Herpå omrøres der først i 10 timer ved stuetemperatur og derefter i 3 timer ved 10 60°C. Derefter inddampes den klare opløsning i rotationsfor damper , og remanensen destilleres i højvakuum. Man får således benzil-di- (2-butoxyethyl) -acetal i fom af en let gullig olie med kp. 180°C/0,002 mm Hg.
Eksempel 9.
15 Fremstilling af benzil-di-(2-phenoxyethyl)-acetal 21 g (0,1 mol) benzil suspenderes i 23,8 g (0,2 mol) thionyl-chlorid og afkøles til 0°C. I løbet af 30 minutter inddryppes der i denne suspension 56 g (0,4 mol) 2-phenoxyethanol, idet temperaturen holdes mellem 2 og 7°C under afkøling. Reaktions-20 blandingen brinqes i løbet af 6 timer på stuetemperatur, hvorved der fås en klar opløsning. Herpå omrøres der først i 10 timer ved stuetemperatur og derefter i 3 timer ved 80°C. Derefter inddampes den klare opløsning først i rotationsfordamper og opvarmes derefter i højvakuum til 180°C. Derved afdestil-25 lerer det ikke omsatte benzil. Remanensen omkrystalliseres af isopropanol. Man får således benzil-di-(2-phenoxyethyl)-acetal i fom af hvide krystaller med smp. 85°C.
Eksempel 10.
Fremstilling af benzil-di-(2-phenylethyl)-acetal 30 Anvender man i stedet for 2-phenoxyethanol en ækvivalent mæng-
Claims (1)
- 2 I 1 Ar -C(OCH2R )2 (I) hvori R^" betyder hydrogen, alkyl med 1-5 C-atomer-, alkenyl med 2 eller 3 C-atomer, aralkyl med 7-9 C-atomer, ar-alkenyl med 8 eller 9 C-atomer eller en gruppe -(CH9) -X, hvor X betyder 2 2 3 3 Δ n 10 halogen, -OR , -SR , -OAr , -SAr , O O -O-C-R^ eller -C-OR^, n et helt tal fra 1-3, R^ sr alkyl med 12 3 1-4 C-atomer, og Ar , Ar og Ar hver for sig betyder en usub-stitueret eller med halogen, alkyl eller -O-alkyl med 1-4 C-atomer eller phenyl højst trisubstitueret phenylgruppe. 15 kendetegnet ved, at man omsætter en aromatisk 1,2-diketon med formlen O O 1 " η o Ar-C-C-Ar (II) 2 hvori Ar og Ar har ovennævnte betydninger, med thionyl-chlorid og en primær alkohol med formlen R^CE^OH, hvori R^ 20 har ovennævnte betydning, idet man gennemfører omsætningen først ved 0 til 20°C og derefter ved 20 til 120°C, fortrinsvis 40 til 100°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK554777A DK147052C (da) | 1972-07-28 | 1977-12-13 | Anvendelse af benzil-monoacetaler som sensibilisatorer til fotopolymerisation af polymerisationsdygtige systemer, der indeholder umaettede forbindelser |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1129572 | 1972-07-28 | ||
| CH1129572A CH575965A5 (en) | 1972-07-28 | 1972-07-28 | Aromatic 1,2-diketone monoacetals - useful as photoinitiators and cross-linking agents |
| CH941773 | 1973-06-28 | ||
| CH941773A CH587867A5 (en) | 1973-06-28 | 1973-06-28 | Aromatic 1,2-diketone monoacetals - useful as photoinitiators and cross-linking agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DK152726B true DK152726B (da) | 1988-05-02 |
| DK152726C DK152726C (da) | 1988-10-24 |
Family
ID=25704784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK416373A DK152726C (da) | 1972-07-28 | 1973-07-27 | Fremgangsmaade til fremstilling af monoacetaler af aromatiske 1,2-diketoner |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4190602A (da) |
| JP (1) | JPS5756456B2 (da) |
| DD (1) | DD105438A5 (da) |
| DE (3) | DE2365497C2 (da) |
| DK (1) | DK152726C (da) |
| ES (1) | ES417307A1 (da) |
| FI (1) | FI60194C (da) |
| FR (1) | FR2194698B1 (da) |
| GB (1) | GB1390006A (da) |
| IT (1) | IT995086B (da) |
| NL (1) | NL7310297A (da) |
| SE (1) | SE417426B (da) |
| SU (2) | SU508173A3 (da) |
Families Citing this family (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4160794A (en) * | 1974-12-24 | 1979-07-10 | Ciba-Geigy Corporation | 1-Oxo-2,2-[dialkylphosphono(alkyl)alkyloxy]-1,2-diphenylethane |
| US4287367A (en) | 1976-04-14 | 1981-09-01 | Basf Aktiengesellschaft | Manufacture of symmetrical or unsymmetrical monoacetals of aromatic 1,2-diketones |
| DE2616408A1 (de) * | 1976-04-14 | 1977-11-03 | Basf Ag | Durch uv-bestrahlung polymerisierbare gemische |
| FR2348180A1 (fr) * | 1976-04-14 | 1977-11-10 | Basf Ag | Procede de preparation de monoacetals de 1,2-dicetones aromatiques et utilisation de ces substances comme photo-inducteurs pour des melanges durcissables sous l'action de radiations |
| CH611633A5 (da) * | 1977-03-16 | 1979-06-15 | Espe Pharm Praep | |
| EP0002707B1 (de) | 1977-12-22 | 1982-04-07 | Ciba-Geigy Ag | Neue Aminoalkyl-benzilketale und ihre Verwendung als Initiatoren für die Photopolymerisation ungesättigter Verbindungen |
| IT1130074B (it) * | 1979-04-20 | 1986-06-11 | Hoffmann La Roche | Composti policiclici e procedimento per la loro preparazione |
| US4351708A (en) | 1980-02-29 | 1982-09-28 | Ciba-Geigy Corporation | Photochemically or thermally polymerizable mixtures |
| DE3008411A1 (de) * | 1980-03-05 | 1981-09-10 | Merck Patent Gmbh, 6100 Darmstadt | Neue aromatisch-aliphatische ketone, ihre verwendung als photoinitiatoren sowie photopolymerisierbare systeme enthaltend solche ketone |
| FR2489336B1 (fr) | 1980-09-04 | 1985-09-13 | Rhone Poulenc Spec Chim | Procede de preparation de polymeres ou copolymeres hydrosolubles a poids moleculaire eleve et a faible teneur en monomere(s) residuel(s), a partir de monomeres olefiniquement insatures |
| IT1147805B (it) * | 1982-01-22 | 1986-11-26 | Lamberti Flli Spa | Metodo per la preparazione di monoacetali simmetrici degli 1,2-dichetoni aromatici a partire dai corrispondenti alfa idrossi chetoni |
| US4518676A (en) * | 1982-09-18 | 1985-05-21 | Ciba Geigy Corporation | Photopolymerizable compositions containing diaryliodosyl salts |
| DE3512179A1 (de) * | 1985-04-03 | 1986-12-04 | Merck Patent Gmbh, 6100 Darmstadt | Fotoinitiatoren fuer die fotopolymerisation in waessrigen systemen |
| KR910000199B1 (ko) * | 1986-04-15 | 1991-01-23 | 시바-가이기 코오포레이숀 | 액체 광개시제 혼합물 |
| US5288917A (en) * | 1986-04-15 | 1994-02-22 | Ciba-Geigy Corporation | Liquid photoinitiator mixtures |
| GB8715435D0 (en) * | 1987-07-01 | 1987-08-05 | Ciba Geigy Ag | Forming images |
| US5095044A (en) * | 1987-08-27 | 1992-03-10 | Ciba-Geigy Corporation | Oligomeric benzil ketals and their use as photoinitiators |
| US4950795A (en) * | 1987-08-27 | 1990-08-21 | Ciba-Geigy Corporation | Oligomeric benzil ketals and their use as photoinitiators |
| DE3834029A1 (de) * | 1988-10-06 | 1990-04-12 | Basf Ag | Verfahren zur herstellung von symmetrischen und unsymmetrischen monoacetalen aromatischer 1,2-diketone |
| US5081307A (en) * | 1989-07-14 | 1992-01-14 | Kawaguchi Chemical Co., Ltd. | Process for preparing 2,2-dimethoxy-2-phenylacetophenone |
| US5167972A (en) * | 1990-09-04 | 1992-12-01 | Wm. Wrigley Jr. Company | Method of stabilizing peptide sweeteners in cinnamon-flavored chewing gums and confections |
| US5139793A (en) * | 1990-07-10 | 1992-08-18 | Wm. Wrigley Jr. Company | Method of prolonging flavor in chewing gum by the use of cinnamic aldehyde propylene glycol acetal |
| US5277919A (en) * | 1990-09-04 | 1994-01-11 | Wm. Wrigley Jr. Company | Method of stabilizing peptide sweeteners in chewing gums and confections with benzaldehyde acetals |
| AU6916394A (en) * | 1993-06-04 | 1995-01-03 | Henkel Corporation | Citral acetal ethers of alpha-hydroxy phenyl ketones and polymerizable compositions |
| US6709742B2 (en) | 1998-05-18 | 2004-03-23 | Dow Global Technologies Inc. | Crosslinked elastic fibers |
| WO2003008680A1 (en) * | 2001-07-17 | 2003-01-30 | Dow Global Technologies Inc. | Elastic bicomponent and biconstituent fibers, and methods of making cellulosic structures from the same |
| JP4967378B2 (ja) * | 2005-03-29 | 2012-07-04 | セイコーエプソン株式会社 | インク組成物 |
| AR058496A1 (es) | 2005-10-26 | 2008-02-06 | Dow Global Technologies Inc | Articulos elasticos de multiples capas |
| US8153243B2 (en) | 2005-12-09 | 2012-04-10 | Dow Global Technologies Llc | Interpolymers suitable for multilayer films |
| US20080132599A1 (en) | 2006-11-30 | 2008-06-05 | Seiko Epson Corporation. | Ink composition, two-pack curing ink composition set, and recording method and recorded matter using these |
| JP5472670B2 (ja) | 2007-01-29 | 2014-04-16 | セイコーエプソン株式会社 | インクセット、インクジェット記録方法及び記録物 |
| US8894197B2 (en) * | 2007-03-01 | 2014-11-25 | Seiko Epson Corporation | Ink set, ink-jet recording method, and recorded material |
| EP2028241A1 (en) * | 2007-08-09 | 2009-02-25 | Seiko Epson Corporation | Photocurable ink composition, ink cartridge, inkjet recording method and recorded matter |
| JP4816976B2 (ja) * | 2007-08-09 | 2011-11-16 | セイコーエプソン株式会社 | 光硬化型インク組成物 |
| JP4766281B2 (ja) * | 2007-09-18 | 2011-09-07 | セイコーエプソン株式会社 | インクジェット記録用非水系インク組成物、インクジェット記録方法および記録物 |
| JP2009269397A (ja) | 2008-02-29 | 2009-11-19 | Seiko Epson Corp | 不透明層の形成方法、記録方法、インクセット、インクカートリッジ、記録装置 |
| US8048976B2 (en) | 2008-09-04 | 2011-11-01 | Amyris, Inc. | Polyfarnesenes |
| JP5692490B2 (ja) * | 2010-01-28 | 2015-04-01 | セイコーエプソン株式会社 | 水性インク組成物、およびインクジェット記録方法ならびに記録物 |
| JP2011152747A (ja) * | 2010-01-28 | 2011-08-11 | Seiko Epson Corp | 水性インク組成物、およびインクジェット記録方法ならびに記録物 |
| US9068024B2 (en) | 2011-02-02 | 2015-06-30 | Toyo Gosei Co., Ltd. | 2,2-dimethoxy-1,2-DI[4-(meth)acryloyloxy]phenylethane-1-one, method for producing the same, radical polymerization initiator and photocurable composition |
| WO2014050551A1 (ja) | 2012-09-28 | 2014-04-03 | 富士フイルム株式会社 | 硬化性樹脂組成物、水溶性インク組成物、インクセットおよび画像形成方法 |
| JP6537118B2 (ja) | 2013-08-07 | 2019-07-03 | 東洋合成工業株式会社 | 化学増幅フォトレジスト組成物及び装置の製造方法 |
| EP2886595B1 (en) * | 2013-12-20 | 2016-04-20 | Borealis AG | Polyolefin composition for medium/high/extra high voltage cables comprising benzil-type voltage stabiliser |
| PL2927302T3 (pl) | 2014-04-03 | 2019-08-30 | Basf Se | Środki ogniochronne na bazie podstawionych związków di-, tri- i tetraaryloetanu |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD75637A (da) * | ||||
| DD75638A (da) * | ||||
| DE1051269B (de) * | 1953-03-11 | 1959-02-26 | Union Carbide Corp | Verfahren zur Herstellung von 1,1,3-Tri-(2-halogen-alkoxy)-alkanen |
| DE1923266U (de) | 1965-06-11 | 1965-09-09 | Simon Fritz | Segelspreizlatte. |
| DE1923266B2 (de) * | 1969-05-07 | 1977-09-29 | Basf Ag, 6700 Ludwigshafen | Alpha-hydroxymethylbenzoinaether |
| US3689565A (en) * | 1970-05-04 | 1972-09-05 | Horst Hoffmann | {60 -methylolbenzoin ethers |
| US3728377A (en) * | 1972-06-05 | 1973-04-17 | Eastman Kodak Co | 4,4-bis(alkoxycarbonyl)benzoin ethers |
-
1973
- 1973-07-11 FI FI2211/73A patent/FI60194C/fi active
- 1973-07-12 SE SE7309792A patent/SE417426B/sv unknown
- 1973-07-24 NL NL7310297A patent/NL7310297A/xx not_active Application Discontinuation
- 1973-07-25 DE DE2365497A patent/DE2365497C2/de not_active Expired
- 1973-07-25 DE DE2365852A patent/DE2365852C3/de not_active Expired
- 1973-07-25 DE DE2337813A patent/DE2337813C3/de not_active Expired
- 1973-07-26 SU SU1953510A patent/SU508173A3/ru active
- 1973-07-26 DD DD172542A patent/DD105438A5/xx unknown
- 1973-07-27 DK DK416373A patent/DK152726C/da not_active IP Right Cessation
- 1973-07-27 GB GB3584473A patent/GB1390006A/en not_active Expired
- 1973-07-27 ES ES417307A patent/ES417307A1/es not_active Expired
- 1973-07-27 FR FR7327634A patent/FR2194698B1/fr not_active Expired
- 1973-07-27 IT IT27241/73A patent/IT995086B/it active
- 1973-07-28 JP JP48085362A patent/JPS5756456B2/ja not_active Expired
-
1974
- 1974-06-20 SU SU742035589A patent/SU751329A3/ru active
-
1978
- 1978-06-22 US US05/919,580 patent/US4190602A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE2337813A1 (de) | 1974-02-07 |
| DE2365852C3 (de) | 1981-10-15 |
| DE2365852B2 (de) | 1981-02-19 |
| SU751329A3 (ru) | 1980-07-23 |
| FI60194C (fi) | 1981-12-10 |
| DK152726C (da) | 1988-10-24 |
| AU5830773A (en) | 1975-01-23 |
| GB1390006A (en) | 1975-04-09 |
| FR2194698B1 (da) | 1976-09-17 |
| DE2365497C2 (de) | 1985-03-21 |
| FR2194698A1 (da) | 1974-03-01 |
| DE2365852A1 (de) | 1976-08-26 |
| JPS5756456B2 (da) | 1982-11-30 |
| US4190602B1 (da) | 1987-05-19 |
| FI60194B (fi) | 1981-08-31 |
| ES417307A1 (es) | 1976-06-01 |
| DE2337813B2 (de) | 1976-07-22 |
| DE2365497A1 (de) | 1975-04-24 |
| US4190602A (en) | 1980-02-26 |
| JPS4955646A (da) | 1974-05-30 |
| SE417426B (sv) | 1981-03-16 |
| NL7310297A (da) | 1974-01-30 |
| SU508173A3 (ru) | 1976-03-25 |
| DD105438A5 (da) | 1974-04-20 |
| IT995086B (it) | 1975-11-10 |
| DE2337813C3 (de) | 1981-11-19 |
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| PBP | Patent lapsed |