DE1009634B - Process for the preparation of 2-oxo-1,3,2-dioxaphospholanes and 2-oxo-1,3,2-dioxaphosphorinanes - Google Patents
Process for the preparation of 2-oxo-1,3,2-dioxaphospholanes and 2-oxo-1,3,2-dioxaphosphorinanesInfo
- Publication number
- DE1009634B DE1009634B DEU3048A DEU0003048A DE1009634B DE 1009634 B DE1009634 B DE 1009634B DE U3048 A DEU3048 A DE U3048A DE U0003048 A DEU0003048 A DE U0003048A DE 1009634 B DE1009634 B DE 1009634B
- Authority
- DE
- Germany
- Prior art keywords
- oxo
- theory
- chloro
- dioxaphosphorinane
- mol
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 8
- XBRCCZCKPZJGEG-UHFFFAOYSA-N 1,3,2lambda5-dioxaphosphinane 2-oxide Chemical class O=P1OCCCO1 XBRCCZCKPZJGEG-UHFFFAOYSA-N 0.000 title claims description 5
- VJRYWXNPDKUNNG-UHFFFAOYSA-N 1,3,2lambda5-dioxaphospholane 2-oxide Chemical class O=P1OCCO1 VJRYWXNPDKUNNG-UHFFFAOYSA-N 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- HWSUUGHIDOOOOJ-UHFFFAOYSA-N dioxaphosphinane Chemical compound C1COOPC1 HWSUUGHIDOOOOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 5
- 150000001447 alkali salts Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- UDNWWDKGKIGFKO-UHFFFAOYSA-N 2-chloro-5-ethyl-4-propyl-1,3,2$l^{5}-dioxaphosphinane 2-oxide Chemical compound CCCC1OP(Cl)(=O)OCC1CC UDNWWDKGKIGFKO-UHFFFAOYSA-N 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- DAZDEYYKPYLVRZ-UHFFFAOYSA-N 2-bromo-1,3,2lambda5-dioxaphospholane 2-oxide Chemical class BrP1(OCCO1)=O DAZDEYYKPYLVRZ-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- CKQBVICKGPLUFZ-UHFFFAOYSA-N 2-chloro-4-methyl-1,3,2$l^{5}-dioxaphosphinane 2-oxide Chemical compound CC1CCOP(Cl)(=O)O1 CKQBVICKGPLUFZ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- LABRPRANVKSMGP-UHFFFAOYSA-N 1,3,2-dioxaphosphinane Chemical compound C1COPOC1 LABRPRANVKSMGP-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SCSGSYNJAFAKKV-UHFFFAOYSA-N 2-chloro-4,6-dimethyl-1,3,2$l^{5}-dioxaphosphinane 2-oxide Chemical compound CC1CC(C)OP(Cl)(=O)O1 SCSGSYNJAFAKKV-UHFFFAOYSA-N 0.000 description 1
- XVQDRCICIUAEDE-UHFFFAOYSA-N 2-chloro-4-methyl-1,3,2$l^{5}-dioxaphospholane 2-oxide Chemical compound CC1COP(Cl)(=O)O1 XVQDRCICIUAEDE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal bicarbonate Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical compound C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 description 1
- 150000004850 phospholanes Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 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
- C07F9/547—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
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
DEUTSCHESGERMAN
Die Erfindung betrifft ein Verfahren zur Herstellung von 2-Oxo-l, 3, 2-dioxaphospholanen und 2-Oxo-l,3,2-dioxaphosphorinanen der allgemeinen FormelnThe invention relates to a process for the preparation of 2-oxo-1,3,2-dioxaphospholanes and 2-oxo-1,3,2-dioxaphosphorinanes the general formulas
Verfahren zur HerstellungMethod of manufacture
von 2-Oxo-l,3,2-dioxaphospholanenof 2-oxo-1,3,2-dioxaphospholanes
und 2-Oxo-l, 3,2-dioxaphosphorinanenand 2-oxo-1,3,2-dioxaphosphorinanes
R1 R 1
-O-O
-O-O
-O-O
R1 R 1
C-C-
-O-O
R3 R 3
-o-O
R2 R 2
-0-0
Anmelder:Applicant:
Union Carbide and Carbon Corporation,
New York, N. Y. (V. St. A.)Union Carbide and Carbon Corporation,
New York, NY (V. St. A.)
Vertreter: Dr.-Ing. A. von KreislerRepresentative: Dr.-Ing. A. von Kreisler
und Dr.-Ing. K. Schönwald, Patentanwälte,and Dr.-Ing. K. Schönwald, patent attorneys,
Köln 1, DeichmannhausCologne 1, Deichmannhaus
Beanspruchte Priorität:
V. St. v. Amerika vom 27. Oktober 1963Claimed priority:
V. St. v. America October 27, 1963
William Morton Lanham, Charleston, W.Va. (V. St. A.), ist als Erfinder genannt wordenWilliam Morton Lanham, Charleston, W.Va. (V. St. A.), has been named as the inventor
in denen R, R1, R2, R3 und R4 Wasserstoffatome oder Alkylgruppen bedeuten, das dadurch gekennzeichnet ist, daß man die entsprechenden 2-Chlor- oder 2-Brom-2-oxo-I13,2-dioxaphospholane bzw. 2-Chlor- oder 2-Brom-2-oxo-l, 3,2-dioxaphosphorinane entweder mit einem wasserfreien Alkalisalz einer gesättigten aliphatischen Carbonsäure in Gegenwart eines inerten Lösungsmittels bei 50 bis 200° oder mit Wasser bei 10 bis 60° in Gegenwart einer Base, insbesondere Pyridin, umsetzt.in which R, R 1 , R 2 , R 3 and R 4 denote hydrogen atoms or alkyl groups, which is characterized in that the corresponding 2-chloro- or 2-bromo-2-oxo-I 1 3,2-dioxaphospholanes or 2-chloro- or 2-bromo-2-oxo-1,3,2-dioxaphosphorinane either with an anhydrous alkali salt of a saturated aliphatic carboxylic acid in the presence of an inert solvent at 50 to 200 ° or with water at 10 to 60 ° in the presence a base, in particular pyridine, is reacted.
Bei der erstgenannten Ausführungsform des Verfahrens wird der phosphorhaltige Reaktionsteilnehmer, vorzugsweise langsam oder tropfenweise, zu einer Suspension des wasserfreien Alkalisalzes der gesättigten aliphatischen Carbonsäure, die eine Mono-, Di- oder Tricarbonsäure sein kann, in einem wasserfreien Lösungsmittel für das gebildete Pyrophosphat gegeben, bis etwa 1 Mol des phosphorhaltigen Reaktionsteilnehmers auf jedes molekulare Äquivalent des Alkalisalzes kommt. Die Umsetzung wird vorzugsweise bei Temperaturen zwischen 50 und 100° durchgeführt. Das Reaktionsgemisch wird dann mit Wasser und verdünnter wäßriger Alkalibicarbonatlösung gewaschen, die dabei gebildete ölige Schicht abgetrennt und bei einer Kolbentemperatur von etwa 100° unter einem Druck von weniger als 2 mm vom Lösungsmittel und den letzten Spuren Wasser abgestreift. Der Rückstand ist praktisch rein.In the first-mentioned embodiment of the process, the phosphorus-containing reactant is preferred slowly or dropwise, to a suspension of the anhydrous alkali salt of the saturated aliphatic Carboxylic acid, which can be a mono-, di- or tricarboxylic acid, in an anhydrous solvent for the pyrophosphate formed added to about 1 mole of the phosphorus-containing reactant for each molecular Equivalent of the alkali salt comes. The reaction is preferably carried out at temperatures between 50 and 100 ° carried out. The reaction mixture is then mixed with water and dilute aqueous alkali metal bicarbonate solution washed, the oily layer formed thereby separated and at a flask temperature of about 100 ° stripped of the solvent and the last traces of water under a pressure of less than 2 mm. The residue is practically pure.
Gemäß der zweiten Ausführungsform des Verfahrens werden die 2-Halogen-2-oxo-l, 3, 2-dioxaphosphorinane
oder -dioxaphospholane mit Wasser bei Temperaturen von 10 bis 60° in Gegenwart einer genügenden Menge
einer Base, vorzugsweise Pyridin, die den gebildeten Chlorwasserstoff aufnimmt, umgesetzt.
Das Reaktionsgemisch wird filtriert und das Filtrat mit verdünnter wäßriger Bicarbonatlösung und mit
Wasser gewaschen. Das gewaschene Filtrat wird bei einer Kolbentemperatur und einem absoluten Druck von
weniger als 2 mm abgestreift. Der zurückbleibende Pyrophosphatabkömmling wird in sehr reiner Form gewonnen.According to the second embodiment of the process, the 2-halo-2-oxo-l, 3, 2-dioxaphosphorinane or -dioxaphospholane with water at temperatures of 10 to 60 ° in the presence of a sufficient amount of a base, preferably pyridine, the hydrogen chloride formed absorbs, implemented.
The reaction mixture is filtered and the filtrate is washed with dilute aqueous bicarbonate solution and with water. The washed filtrate is stripped off at a flask temperature and an absolute pressure of less than 2 mm. The remaining pyrophosphate derivative is obtained in a very pure form.
Von den Salzen gesättigter aliphatischer Carbonsäuren, die sich zur Herstellung der neuen Verbindungen eignen, seien die Alkali- und Ammoniumsalze der Fettsäuren mit 1 bis 18 Kohlenstoffatomen, wie Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Capronsäure, 2-Äthylcapronsäure, Caprinsäure, Palmitinsäure und Stearinsäure, genannt, von den zweiwertigen Salzen die der Oxalsäure, Glutarsäure, Bernsteinsäure, Adipinsäure, n-Pimelinsäure und Sebacinsäure; von den dreibasischen Salzen die der Tricarballylsäure.Of the salts of saturated aliphatic carboxylic acids, which are suitable for the preparation of the new compounds, be the alkali and ammonium salts of fatty acids with 1 to 18 carbon atoms, such as formic acid, acetic acid, Propionic acid, butyric acid, caproic acid, 2-ethylcaproic acid, capric acid, palmitic acid and stearic acid, called, of the divalent salts those of oxalic acid, glutaric acid, succinic acid, adipic acid, n-pimelic acid and sebacic acid; of the tribasic salts that of tricarballylic acid.
Die als Ausgangsmaterial dienenden 2-Halogen-2-oxo-1, 3, 2-dioxaphosphorinan- und entsprechenden Phospholanabkömmlinge werden gemäß einem älteren Vorschlag gewöhnlich durch Umsetzung von Alkan-1, 3-diolen oder Alkan-1,2-diolen mit Phosphorylchlorid oder -bromid hergestellt.The 2-halo-2-oxo-1, 3, 2-dioxaphosphorinane and corresponding phospholane derivatives used as starting material are usually according to an older proposal by reacting alkane-1, 3-diols or Alkane-1,2-diols with phosphoryl chloride or bromide manufactured.
Die verfahrensgemäß hergestellten 2-Oxo-l, 3, 2-dioxaphospholane und 2-Oxo-l, 3, 2-dioxaphosphorinane eignen sich als Weichmacher und als Färbereihüfsmittel. Sie sind nur schwer hydrolysierbar.The 2-oxo-1,3,2-dioxaphospholanes produced according to the process and 2-oxo-1,3,2-dioxaphosphorinanes are suitable as plasticizers and as dyeing auxiliaries. she are difficult to hydrolyze.
709 547/434709 547/434
In den folgenden Beispielen ist das Verfahren gemäß der Erfindung näher erläutert.The process according to the invention is explained in more detail in the following examples.
Zu einer Suspension von 90 g (1,1 Mol) wasserfreiem Natriumacetat in 400 g Toluol werden während 20 Minuten unter Rühren tropfenweise 277 g (1 Mol) 2-Chlor-5-äthyl-2-oxo-4-propyl-l, 3, 2-dioxaphosphorinan unter Aufrechterhaltung einer Temperatur der Reaktionsmischung von 100° gegeben und die Reaktionsmischung danach noch weitere 30 Minuten auf dieser Temperatur gehalten. Danach wird die Reaktionsmischung zunächst mit 800 ecm Wasser, dann zweimal mit verdünnter wäßriger Natriumbicarbonatlösung und noch zweimal mit Wasser gewaschen. Die ausgeschiedene ölige Schicht wird abgetrennt und bei einer Kolbentemperatur von 100° und einem Druck von weniger als 2 mm abgestreift. Es bleibt 5, 5'-Diäthyl-2, 2'-dioxo-4,4'-dipropyl-pyro-l, 3,2-dioxaphosphorinan der FormelTo a suspension of 90 g (1.1 mol) of anhydrous sodium acetate in 400 g of toluene are added over 20 minutes with stirring, dropwise 277 g (1 mol) of 2-chloro-5-ethyl-2-oxo-4-propyl-1,3,2-dioxaphosphorinane while maintaining given a temperature of the reaction mixture of 100 ° and then the reaction mixture held at this temperature for a further 30 minutes. Thereafter, the reaction mixture is initially at 800 ecm Water, then washed twice with dilute aqueous sodium bicarbonate solution and twice more with water. The precipitated oily layer is separated and at a flask temperature of 100 ° and stripped at a pressure of less than 2 mm. There remains 5, 5'-diethyl-2, 2'-dioxo-4,4'-dipropyl-pyro-l, 3,2-dioxaphosphorinane the formula
1, 3, 2-dioxaphosphorinan mit 1,1 Mol wasserfreiem Natriumacetat in 400 g Toluol eine 97°/0ige Ausbeute von 5,5'-Dibutyl-5, 5'-diäthyl-2, 2'-dioxo-pyro-l, 3, 2-dioxaphosphorinan 1, 3, 2-dioxaphosphorinane with 1.1 mol of anhydrous sodium acetate in 400 g of toluene, a 97 ° / 0 yield of 5,5'-dibutyl-5, 5'-diethyl-2, 2'-dioxo-pyro-l , 3, 2-dioxaphosphorinane
JjL Q V-/£ v/ — \^2 -tJ-5JjL Q V- / £ v / - \ ^ 2 -tJ-5
-O O-O O
\ll\ ll
P-P-
/ -o/ -o
-O-O
-O-O
H5C2—Cs H 5 C 2 -C s
-o-O
C3H7 C 3 H 7
-O-O
als gelbe Flüssigkeit mit folgenden Eigenschaften zurück: n% = 1..4657, spezifisches Gewicht 25/15 = 1,174, Molekulargewicht (ebulioskopisch bestimmt) = 374,9 (Theorie = 398,4); P = 15,51 % (Theorie = 15,55 %), C = 48,53 % (Theorie = 48,23 %), H = 8,11 % (Theorie = 8,10%). Die Ausbeute, bezogen am die zur Herstellung des 2-Chlor-5-äthyl-2-oxo-4-propyl-l, 3,2-dioxaphosphorinans verwendete Menge Phosphorylchlorid, beträgt 89 %.returned as a yellow liquid with the following properties: n% = 1..4657, specific weight 25/15 = 1.174, molecular weight (determined ebulioscopy) = 374.9 (theory = 398.4); P = 15.51% (theory = 15.55%), C = 48.53% (theory = 48.23%), H = 8.11% (theory = 8.10%). The yield, based on the amount of phosphoryl chloride used to prepare the 2-chloro-5-ethyl-2-oxo-4-propyl-1,3,2-dioxaphosphorinane, is 89%.
Zu einer auf 100° erwärmten Suspension von 53 g (0,65 Mol) wasserfreiem Natriumacetat in 300 g Toluol werden unter Rühren langsam während 15 Minuten 100 g (0,639 Mol) 2-Chlor-4-methyl-2-oxo-l, 3, 2-dioxaphospholan gegeben. Nachdem das Reaktionsgemisch weitere 30 Minuten bei dieser Temperatur gehalten wurde, wird sie zu einer Mischung aus 200 ecm trockenem Aceton und 30 g Kieselgur gegeben, und dann wird die Mischung filtriert. Das FJtrat wird bei einer Kolbentemperatur von 100° und einem Druck von weniger als 2 mm abgestreift. Es bleibt 4, 4'-Dimethyl-2, 2'-dioxo-pyro-l, 3, 2-dioxaphospholan To a suspension, heated to 100 °, of 53 g (0.65 mol) of anhydrous sodium acetate in 300 g of toluene 100 g (0.639 mol) of 2-chloro-4-methyl-2-oxo-1,3,2-dioxaphospholane are slowly added with stirring over a period of 15 minutes given. After the reaction mixture has been kept at this temperature for a further 30 minutes, is they are added to a mixture of 200 ecm of dry acetone and 30 g of diatomaceous earth, and then the mixture is filtered. The filtrate is stripped off at a piston temperature of 100 ° and a pressure of less than 2 mm. There remains 4,4'-dimethyl-2, 2'-dioxo-pyro-1,3,2-dioxaphospholane
:H H : HH
-O-O
-O-O
CHS CH S
-O-O
in einer Ausbeute von 85% in Form einer braunen, wässerlöslichen, chlorfreien Flüssigkeit zurück, die folgende Eigenschaften hat: Äquivalentgewicht (bestimmt durch Verseifung) = 69,5 (Theorie = 64,5); C = 27,07%, H 5llin a yield of 85% in the form of a brown, water-soluble, chlorine-free liquid, the following Has properties: equivalent weight (determined by saponification) = 69.5 (theory = 64.5); C = 27.07%, H 5ll
in Form eines breiförmigen Rückstandes folgender Analyse: P = 14,25% (Theorie = 14,53%), C = 51,5% (Theorie = 50,71 %), H = 8,8 % (Theorie = 8,5 %), Äquivalentgewicht (bestimmt durch Verseifung) = 200 ao (Theorie = 213).in the form of a pulpy residue following analysis: P = 14.25% (theory = 14.53%), C = 51.5% (Theory = 50.71%), H = 8.8% (theory = 8.5%), equivalent weight (determined by saponification) = 200 ao (theory = 213).
Gemäß der Arbeitsanweisung des Beispiels 1 wird 1 Mol 2-Chlor-5, 5-diäthyl-2-oxo-l, 3, 2-dioxaphosphorinan mit 1,1 Mol wasserfreiem Natriumacetat in 400 g Toluol umgesetzt. Nach Zusatz von 200 ecm Wasser trennt sich das Reaktionsgemisch in eine ölige Schicht und eine wäßrige Schicht, in der ein Feststoff suspendiert ist. Die wäßrige Schicht wird nitriert, und es werden als Filterrückstand 101 g weiße Kristalle erhalten, die bis zur Chlorfreiheit mit Wasser gewaschen werden. Die ölige Schicht wird mit 800 ecm Wasser gewaschen und dann die gewaschene Schicht bei einer Kolbentemperatur von 60° und einem Druck von weniger als 2 mm abgestreift. Der Rückstand wird durch Auflösen in 200 ecm trockenem Aceton und Ausfällen mit 500 ecm destilliertem Wasser gereinigt. Der weiße kristalline Niederschlag wird abfiltriert und mit den 101 g früher erhaltenen feuchten Kristallen vereinigt und getrocknet. Es wird in 85%iger Ausbeute 2, 2'-Dioxo-5, 5, 5', 5'-tetraäthyl-pyro-1, 3, 2-dioxaphosphorinanAccording to the instructions in Example 1, 1 mole of 2-chloro-5, 5-diethyl-2-oxo-l, 3, 2-dioxaphosphorinane is used reacted with 1.1 mol of anhydrous sodium acetate in 400 g of toluene. After adding 200 ecm of water the reaction mixture separates into an oily layer and an aqueous layer in which a solid is suspended is. The aqueous layer is nitrided, and 101 g of white crystals are obtained as the filter residue, which are up to be washed with water to ensure freedom from chlorine. The oily layer is washed with 800 ecm of water and then the washed layer is stripped off at a bulb temperature of 60 ° and a pressure of less than 2 mm. The residue is distilled by dissolving in 200 ecm dry acetone and precipitating with 500 ecm Water purified. The white crystalline precipitate is filtered off and obtained earlier with the 101 g wet crystals combined and dried. It is in 85% yield 2, 2'-dioxo-5, 5, 5 ', 5'-tetraethyl-pyro-1, 3, 2-dioxaphosphorinane
O OO O
H5C2—C—C2H5 H 5 C 2 -C C 2 H 5
Q Q
-O-O
mit folgenden Eigenschaften erhalten: Kp. 182 bis 190°, Reinheitsgrad (bestimmt durch Verseifung) = 98,4%; P = 17,10% (Theorie = 16,72%), C = 45,45% (Theorie = 45,40 %), H = 7,60% (Theorie = 7,62%).obtained with the following properties: b.p. 182 to 190 °, degree of purity (determined by saponification) = 98.4%; P = 17.10% (theory = 16.72%), C = 45.45% (theory = 45.40%), H = 7.60% (theory = 7.62%).
Unter den Reaktionsbedingungen des Beispiels 1 ergibt die Umsetzung von 1 Mol S-ButyL^-chlor-S-äthyl^-oxo-Under the reaction conditions of Example 1, the reaction of 1 mole of S-ButyL ^ -chlor-S-ethyl ^ -oxo-
Zu einer auf 100° erwärmten Suspension von 83 g (1,01 Mol) wasserfreiem Natriumacetat in 400 g Toluol werden unter Rühren tropfenweise während 20 Minuten 171 g (1 Mol) 2-Chlor-4-methyl-2-oxo-l, 3, 2-dioxaphosphorinan gegeben. Nachdem die Reaktionsmischung weitere 30 Minuten bei dieser Temperatur stehengelassen wurde, wird sie mit 30 g Kieselgur gemischt und filtriert. Das Filtrat wird bei einer Kolbentemperatur von 100° und einem Druck von weniger als 2 mm abgestreift. DerTo a suspension, heated to 100 °, of 83 g (1.01 mol) of anhydrous sodium acetate in 400 g of toluene 171 g (1 mol) of 2-chloro-4-methyl-2-oxo-1,3,2-dioxaphosphorinane are added dropwise with stirring over a period of 20 minutes given. After the reaction mixture was left to stand at this temperature for a further 30 minutes it is mixed with 30 g of diatomaceous earth and filtered. The filtrate is at a flask temperature of 100 ° stripped and a pressure of less than 2 mm. Of the
lohfarbene feste Rückstand ist 4, 4'-Dimethyl-2, 2'-dioxo-pyro-1, 3, 2-dioxaphosphorinanThe tan solid residue is 4,4'-dimethyl-2, 2'-dioxo-pyro-1, 3, 2-dioxaphosphorinane
H HH H
C OC O
/c\/ c \
H C-H C-
/ N
H/ N
H
'. P —'. P -
-O-O
CH3 CH 3
-O-O
folgender Analyse: P = 20,75% (Theorie = 21,66%), C = 33,41% (Theorie = 33,75%), H = 5,59% (Theorie = 5,63 %). Die Ausbeute, bezogen auf die zur Herstellung des 2-Chlor-4-methyl-2-oxo-l, 3, 2-dioxaphosphorinans eingesetzte Menge Phosphorylchlorid, beträgt 49%.following analysis: P = 20.75% (theory = 21.66%), C = 33.41% (theory = 33.75%), H = 5.59% (theory = 5.63%). The yield, based on that for the preparation of 2-chloro-4-methyl-2-oxo-1,3,2-dioxaphosphorinane amount of phosphoryl chloride used is 49%.
Nach den Anweisungen des Beispiels 5 wird 1 Mol 2-Chlor-4, 6-dimethyl-2-oxo-l, 3, 2-dioxaphosphorinan mit 1,1 Mol in Toluol suspendiertem, wasserfreiem Natriumacetat umgesetzt. Die Reaktionsmischung wird filtriert. Nachdem das Aceton unter Vakuum entfernt wurde, werden 84 g 2, 2'-Dioxo-4, 4', 6, 6'-tetramethylpyro-1, 3, 2-dioxaphosphorinanAccording to the instructions in Example 5, 1 mol of 2-chloro-4,6-dimethyl-2-oxo-1,3,2-dioxaphosphorinane is used reacted with 1.1 mol of anhydrous sodium acetate suspended in toluene. The reaction mixture will filtered. After the acetone has been removed under vacuum, 84 g of 2, 2'-dioxo-4, 4 ', 6, 6'-tetramethylpyro-1, 3, 2-dioxaphosphorinane
phosphorinan in Benzol wird innerhalb von 20 Minuten unter Rühren tropfenweise eine Mischung von 5 g (0,278 Mol) Wasser und 45 g (0,57 Mol) Pyridin gegeben. Die Reaktionsmischung wird 6 Stunden auf 40 bis 50° erwärmt, abgekühlt und das Pyridinhydrochlorid abfUtiiert. Das Filtrat wird zunächst mit einer verdünnten wäßrigen Lösung von Natriumbicarbonat und dann mit Wasser bis zur neutralen Reaktion gegenüber Lackmuspapier gewaschen. Nun wird bei einer Kolbentemperatur von 100° und einem Druck von weniger als 2 mm abgestreift. Das 5, 5'-Diäthyl-2, 2'-dioxo-4,4'-dipropyl-pyro-1, 3, 2-dioxaphosphorinanphosphorinane in benzene is added dropwise to a mixture of 5 g within 20 minutes with stirring (0.278 mol) water and 45 g (0.57 mol) pyridine. The reaction mixture is heated to 40 to 50 ° for 6 hours heated, cooled and the pyridine hydrochloride removed. The filtrate is first with a dilute aqueous solution of sodium bicarbonate and then with Water washed until neutral to litmus paper. Now at a bulb temperature stripped of 100 ° and a pressure of less than 2 mm. The 5,5'-diethyl-2, 2'-dioxo-4,4'-dipropyl-pyro-1, 3, 2-dioxaphosphorinane
C2H5-CC 2 H 5 -C
-O O-O O
P-P-
-O-O
CH,CH,
C OC O
C-C-
-O-O
CH3 CH 3
H C-H C-
/ \
H C3H7 / \
HC 3 H 7
wird, berechnet auf den phosphorhaltigen Reaktionsteilnehmer, mit 90%iger Ausbeute in Form einer klaren farblosen Flüssigkeit gewonnen, die folgende Eigenschaften hat: « ^ = 1,4659, Reinheitsgrad = 99% (bestimmt durch Verseifung). Die Verbindung ist chlorfrei und hatis calculated on the phosphorus-containing reactants, with 90% yield in the form of a clear colorless liquid obtained the following properties has: «^ = 1.4659, degree of purity = 99% (determined by saponification). The compound is chlorine-free and has
einen Salzgehalt entsprechend 0,01 ecm 1-normaler Überchlorsäure/g. a salt content corresponding to 0.01 ecm 1-normal superchloric acid / g.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US770419XA | 1953-10-27 | 1953-10-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1009634B true DE1009634B (en) | 1957-06-06 |
Family
ID=22135740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEU3048A Pending DE1009634B (en) | 1953-10-27 | 1954-10-22 | Process for the preparation of 2-oxo-1,3,2-dioxaphospholanes and 2-oxo-1,3,2-dioxaphosphorinanes |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE1009634B (en) |
| GB (1) | GB770419A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2280640A1 (en) * | 1974-07-30 | 1976-02-27 | Sandoz Sa | IGNIFUGATION OF POLYMERIC ORGANIC MATERIALS BY MEANS OF DIOXAPHOSPHORINANE DERIVATIVES |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220057180A (en) * | 2020-10-29 | 2022-05-09 | 솔브레인 주식회사 | Method for preparing symmetric phosphate based compound |
-
1954
- 1954-10-19 GB GB30018/54A patent/GB770419A/en not_active Expired
- 1954-10-22 DE DEU3048A patent/DE1009634B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2280640A1 (en) * | 1974-07-30 | 1976-02-27 | Sandoz Sa | IGNIFUGATION OF POLYMERIC ORGANIC MATERIALS BY MEANS OF DIOXAPHOSPHORINANE DERIVATIVES |
Also Published As
| Publication number | Publication date |
|---|---|
| GB770419A (en) | 1957-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1018870B (en) | Process for the production of phosphoric acid esters | |
| DE2601278C3 (en) | Cyclic Pentaerythritol Diphosphates | |
| DE855567C (en) | Process for the preparation of insecticidal phosphorus compounds | |
| DE1009634B (en) | Process for the preparation of 2-oxo-1,3,2-dioxaphospholanes and 2-oxo-1,3,2-dioxaphosphorinanes | |
| EP0543845B1 (en) | Process for producing aminomethanephosphonic acid and aminomethylphosphinic acids | |
| DE1543531A1 (en) | Process for the preparation of halogenated esters of phosphoric acids | |
| EP0026736B1 (en) | Process for preparing 2,3,5-trichloropyridine and ammonium salts of the methyl ester of methane phosphonic acid, and their preparation | |
| EP0015503B1 (en) | Process for preparing diazinone | |
| DE1104957B (en) | Process for the preparation of optionally substituted dialkylphosphine oxides | |
| EP0022546A2 (en) | Process for the preparation of 1-oxo-phospholanchlorohydrines and some particular ones of these compounds | |
| DE2511932C2 (en) | Process for the preparation of tertiary hydroxyalkylphosphine oxides | |
| DE1052408B (en) | Process for the preparation of cyclic dithiophosphoric acid esters | |
| DE962608C (en) | Process for the production of phosphoric or thiophosphoric acid esters | |
| DE1141634B (en) | Process for the production of dithiolphosphoric acid esters | |
| DE1276633B (en) | Process for the preparation of esters of certain acids of phosphorus | |
| DE1231244C2 (en) | Process for the preparation of esters, ester amides or amides of pyrophosphoric acid or hypophosphorous acid | |
| DE2254062C3 (en) | Process for the preparation of tetrachloroalkyl phosphoric acid ester dichlorides and tetrachloroalkyl thiophosphoric acid ester dichlorides | |
| EP0003553B1 (en) | Method of preparation of o,s-dialkylthiophosphoric acid chlorides | |
| DE957301C (en) | Process for the production of new, phosphorus-containing organic compounds | |
| AT366389B (en) | METHOD FOR PRODUCING NEW N-PHOSPHONOMETHYLGLYCINE TRIESTERS | |
| DE19625167C1 (en) | New bisether containing a 2,2'-biaryl radical and a process for their preparation | |
| DE719830C (en) | Process for the production of salts of higher molecular phosphatidic acids | |
| DE1078558B (en) | Process for the preparation of dialkyl phosphites with dissimilar alkyl groups | |
| DE1216278B (en) | Process for the production of asymmetrical phosphorus acid-O, O-diesters | |
| EP0144743A1 (en) | Process for the preparation of organic chlorophosphanes |