GB782267A - A process for the manufacture of pyrophosphoric and phosphonic acid derivatives - Google Patents
A process for the manufacture of pyrophosphoric and phosphonic acid derivativesInfo
- Publication number
- GB782267A GB782267A GB1336654A GB1336654A GB782267A GB 782267 A GB782267 A GB 782267A GB 1336654 A GB1336654 A GB 1336654A GB 1336654 A GB1336654 A GB 1336654A GB 782267 A GB782267 A GB 782267A
- Authority
- GB
- United Kingdom
- Prior art keywords
- base
- acid
- imino
- chloride
- phosphoric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title abstract 6
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 title abstract 3
- 229940005657 pyrophosphoric acid Drugs 0.000 title abstract 3
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 title 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 title 1
- 239000002585 base Substances 0.000 abstract 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 16
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 abstract 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 8
- 239000002253 acid Substances 0.000 abstract 6
- 150000003839 salts Chemical class 0.000 abstract 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 5
- 239000002904 solvent Substances 0.000 abstract 5
- 150000008064 anhydrides Chemical class 0.000 abstract 4
- 238000006243 chemical reaction Methods 0.000 abstract 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract 3
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 abstract 2
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 abstract 2
- MWGSSMAHEZDRQP-UHFFFAOYSA-N [hydroxy(phenyl)phosphoryl]oxy-phenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)OP(O)(=O)C1=CC=CC=C1 MWGSSMAHEZDRQP-UHFFFAOYSA-N 0.000 abstract 2
- OIRDTQYFTABQOQ-KQYNXXCUSA-N adenosine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O OIRDTQYFTABQOQ-KQYNXXCUSA-N 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 125000003118 aryl group Chemical group 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 2
- -1 cycloalkyl amines Chemical group 0.000 abstract 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 2
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 abstract 2
- 150000003009 phosphonic acids Chemical class 0.000 abstract 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract 2
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 abstract 1
- 239000002126 C01EB10 - Adenosine Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- 230000010933 acylation Effects 0.000 abstract 1
- 238000005917 acylation reaction Methods 0.000 abstract 1
- 229960005305 adenosine Drugs 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 abstract 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 abstract 1
- 230000029936 alkylation Effects 0.000 abstract 1
- 238000005804 alkylation reaction Methods 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 235000010290 biphenyl Nutrition 0.000 abstract 1
- 239000004305 biphenyl Substances 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 235000011180 diphosphates Nutrition 0.000 abstract 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 abstract 1
- 125000001624 naphthyl group Chemical group 0.000 abstract 1
- 239000002777 nucleoside Substances 0.000 abstract 1
- 150000003833 nucleoside derivatives Chemical class 0.000 abstract 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 abstract 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 abstract 1
- 229940048084 pyrophosphate Drugs 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000002151 riboflavin Substances 0.000 abstract 1
- 229960002477 riboflavin Drugs 0.000 abstract 1
- 235000019192 riboflavin Nutrition 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 150000003512 tertiary amines Chemical class 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
- C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
- C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
- C07H19/16—Purine radicals
- C07H19/20—Purine radicals with the saccharide radical esterified by phosphoric or polyphosphoric acids
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/098—Esters of polyphosphoric acids or anhydrides
-
- 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)]
-
- 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)]
- C07F9/3895—Pyrophosphonic acids; phosphonic acid anhydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Anhydrides of phosphoric acid monoesters, anhydrides of phosphonic acids, and mixed anhydrides of phosphoric acid monoesters and phosphonic acids, and salts thereof, are obtained by reacting a phosphoric acid monoester or a phosphonic acid with an imino chloride in the presence of two equivalents of a suitable base and treating the product with a monobasic salt of a phosphoric acid or with either the free phosphoric acid monoester or the free phosphonic acid, (preferably, in the case where the free acid or acid ester is used, in the presence of a further equivalent of a base, which base may be present during the said imino-chloride reaction step) and, if desired, converting the product into the free acid or further salts. The imino chlorides used in the process are those of the general formula (A) (Cl)C=N-B, wherein A and B are organic radicals which are inert under the reaction conditions and wherein A is attached to the carbon atom through a tertiary carbon atom. The preferred imino chlorides are N-alkylbenzimino chlorides. Suitable bases for use in the process are alkali and alkaline earth metal hydroxides or tertiary amines, e.g. tertiary alkyl or cycloalkyl amines. The base should generally be a strong base but when symmetrical products are required either a weak base (e.g. pyridine) or a strong base can be used. A weak base can be used in addition to the base used as reactant, e.g. when the weak base is used as a solvent for the reaction mixture. The process need only be carried out in two steps when an asymmetrical product is being prepared. When a symmetrical product is required the process may be carried out by reacting a phosphoric acid monoester or a phosphonic acid with a monobasic salt of the phosphoric acid monoester or of the phosphonic acid or with the free monoester or phosphonic acid in the presence of the imino chloride and of two or three equivalents of a suitable base. The products are of the type <FORM:0782267/IV (a)/1> wherein m and n are 0 or 1 and may differ from each other and R1 and R11 are aryl or alkyl groups which may contain substituents, e.g. aryl or heterocyclic or hydroxyl substituents, as in the case where R1OH and/or R11OH from which R1 and/or R11 are derived, is benzyl alcohol, riboflavin, adenosine or other nucleoside, or a sugar, and R1 and R11 may be the same or different. Where the starting materials contain reactive hydroxyl groups in the organic part of the molecule the said groups should be protected, e.g. by acylation, alkylation, or acetal formation. The conversion of the products into the free acids may be effected by treatment with a mineral acid or by passage through a cationic exchange resin in its hydrogen form and the further salts may be produced from the free acid by treatment with the appropriate base or from the salt product by double decomposition. During the process the imino chloride is converted into the corresponding amide which may be reconverted to the imino chloride by reacting with phosphorus pentachloride or thionyl chloride and the imino chloride can thus be used again. Examples are given for the production of (a) symmetrical pyrophosphoric acid diphenyl ester from phenyl phosphoric acid using pyridine as solvent and triethylamine as base, the imino chloride used being N-sec.-butyl-, N-methyl-, N-ethyl-, N-isopropyl-, or N-cyclohexyl-benzimino-chloride or by using pyridine alone as base and solvent and N-sec.-butyl-benzimino chloride as the imino chloride; (b) symmetrical pyrophosphoric acid di-(naphthyl-(2)) ester from naphthyl-(2)-phosphoric acid using the solvent, base and imino chlorides as for product (a); (c) phenylphosphonic anhydride from phenylphosphonic acid, the reaction being carried out in pyridine, acetonitrile or a -picoline and with the same base and iminochlorides as for product (a); (d) benzylphosphonic anhydride by replacing the phenyl phosphoric acid used for product (a) with benzyl phosphonic acid; (e) naphthyl-(2)-phosphoric phenylphosphonic anhydride from phenylphosphonic acid in the first stage and naphthyl - (2) - phosphoric acid in the second stage. Each of the products (a) to (e) is recovered in the form of its bis-(S-benzyl-isothiouronium salt). In another example P1,P2-diadenosine-51 pyrophosphate is obtained from adenosine-51-phosphate using dimethyl-octylamine as the base, dimethyl formamide as solvent and either N-sec.-butyl-, or N-phenylbenziminochloride as the imino chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1336654A GB782267A (en) | 1954-05-07 | 1954-05-07 | A process for the manufacture of pyrophosphoric and phosphonic acid derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1336654A GB782267A (en) | 1954-05-07 | 1954-05-07 | A process for the manufacture of pyrophosphoric and phosphonic acid derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB782267A true GB782267A (en) | 1957-09-04 |
Family
ID=10021660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1336654A Expired GB782267A (en) | 1954-05-07 | 1954-05-07 | A process for the manufacture of pyrophosphoric and phosphonic acid derivatives |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB782267A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3388192A (en) * | 1965-04-13 | 1968-06-11 | Squibb & Sons Inc | 3-(fluoromethyl)-3-buten-1-ol pyrophosphate and process for making same |
| FR2517762A1 (en) * | 1981-12-08 | 1983-06-10 | Egelius Goeran | FLUID CONTROL MEANS FOR REVERSIBLE LINEAR MOVEMENT |
-
1954
- 1954-05-07 GB GB1336654A patent/GB782267A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3388192A (en) * | 1965-04-13 | 1968-06-11 | Squibb & Sons Inc | 3-(fluoromethyl)-3-buten-1-ol pyrophosphate and process for making same |
| FR2517762A1 (en) * | 1981-12-08 | 1983-06-10 | Egelius Goeran | FLUID CONTROL MEANS FOR REVERSIBLE LINEAR MOVEMENT |
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