GB978680A - Organic nitrite esters and processes for the preparation of derivatives therefrom - Google Patents

Organic nitrite esters and processes for the preparation of derivatives therefrom

Info

Publication number
GB978680A
GB978680A GB11823/60A GB1182360A GB978680A GB 978680 A GB978680 A GB 978680A GB 11823/60 A GB11823/60 A GB 11823/60A GB 1182360 A GB1182360 A GB 1182360A GB 978680 A GB978680 A GB 978680A
Authority
GB
United Kingdom
Prior art keywords
acetate
prepared
nitrite
amino
formula
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
Application number
GB11823/60A
Inventor
Derek Harold Richard Barton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Scherico Ltd
Original Assignee
Scherico Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Scherico Ltd filed Critical Scherico Ltd
Priority to GB11823/60A priority Critical patent/GB978680A/en
Publication of GB978680A publication Critical patent/GB978680A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/04Preparation of esters of nitrous acid
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C207/00Compounds containing nitroso groups bound to a carbon skeleton
    • C07C207/02Compounds containing nitroso groups bound to a carbon skeleton the carbon skeleton not being further substituted
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/021Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/22Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015Dispersions of solid lubricants
    • C10N2050/02Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Steroid Compounds (AREA)

Abstract

The invention comprises an organic nitrite ester of a condensed ring organic compound in which the nitrite radical is linked to one carbon atom and is conformationally adjacent to a hydrogen atom attached to another carbon atom which is spuced from said one carbon atom by a carbon adjacent the nitrite radical and a carbon, oxygen, sulphur or nitrogen atom, and a process for the preparation of an organic nitroso compound having a skeleton of at least 6 carbon atoms and a further atom selected from the group consisting of carbon, oxygen, sulphur and nitrogen, said nitroso compound including the grouping ON-C-X-C-C-OH wherein X represents a methylene, methylidene or methylidyne group or a nitrogen, oxygen or sulphur atom and/or a compound resulting from the stabilization of the said nitroso compound such as an oxime or a nitrone wherein a nitrite ester having a skeleton consisting of at least 6 carbon atoms and of an atom selected from the groups consisting of carbon, oxygen, sulphur and nitrogen and including the grouping <FORM:0978680/C1/1> wherein ONO is a nitrite group, H is a hydrogen atom conformationally adjacent to such nitrite radical and X has the above significance) is irradiated in solution preferably a substantially water free and substantially oxygen free solution, by ultraviolet radiation the wavelength of which is within the range of from 2,000 to 4,500 A, preferably 3,400 to 4,000 A, to effect the exchange of the NO portion of said nitrite group with said hydrogen atom. The organic nitrites for use in the above process may be prepared by reacting the required organic hydroxy compound with a nitrosyl halide. A large number of suitable organic hydroxy compounds from which the nitrites are obtainable are referred to. Thus the organic nitrite may be an alkyl-, alkene-, alkyne-, aryl-, alicyclic-, heterocyclic- or steroidal-nitrite. The nitrite may also be derived from antibiotics containing a hydroxy group such as penicillin and erythromycin; reserpine; Vitamin A; and terpenes such as nerol, geraniol, citronellol and menthol. The steroidal nitrite may be a 1b ,- 2b -, 4b -, 6b -, 7b -, 11a -, 11b -, 15a -, 18-, 19-, 20a -, 20b - or 24-nitrite steroid compound such as a steroidal nitrite of the estrogen, androgen, methyltestosterone, pregnane, cardiac azlycone, bile acid, chlolesterol, ergosterol or stigmasterol series. In the case of an organic hydroxy compound containing more than one hydroxy group it may be necessary to protect some of the hydroxy groups to avoid reaction with the nitrosyl halide, for example by acylation. The process is useful for the preparation of polyols such as a triol by the following type of process: 1-decanyl-nitrite is formed from 1-decanol, the nitrite is irradiated to form 4-oximino -1- decanol, then acetylated to form the 1-acetate and reduced to the 4-amine -1- acetate, oxidised to decan-diol-1, 4 1-acetate, then to the 4-nitrite 1-acetate which is irradiated to form 7-oximino-1, 4-decandiol 1-acetate and then reduced and oxidised as before, to form decanyl-1, 4, 7-triol 1-acetate and finally decanyl-1, 4, 7-triol. Substituted resperine of the formula <FORM:0978680/C1/2> is prepared by reducing reserpine with lithium aluminium hydride to form a diol of the formula, <FORM:0978680/C1/3> acetylating this compound to form the corresponding diacetate, and selectively hydrolysing the diacetate. 4-Amino -2- methyl-heptanol-1 are prepared and the corresponding trimethyl ammonium iodide by reducing the corresponding 4-oximino compound with sodium and ethanol to form the free 4-amino compound and, when required, treating the product with methyl iodide. By a similar procedure the following are prepared: 4-amino-heptanol-1 and the trimethylammonium sulphonate thereof, 4-amino -1- lauryl alcohol, 4-amino -1- cetyl alcohol, 4-amino -1- stearyl alcohol, 5-amino -2- heptyl alcohol, 6-amino -3- heptyl alcohol, 5-amino-octanol-2 (the three previously mentioned compounds may be treated with sulphuric acid to form the corresponding amino-sulphates), 4-amino -2- ethyl hexanol, and 4-amino-undecenyl alcohol. 4-Keto-octanol-1 is prepared by treating 4-oximino-octanol-1 with acetic acid and aqueous sodium nitrite. By a similar method the following are prepared. 4-keto-undecenyl alcohol, 4-keto-nerol, 3-b -hydroxyethyl-cyclohexanone, 4-hydroxy-cycloheptanone, 4-hydroxy-cyclo-octanone, tropine ketone of the formula <FORM:0978680/C1/4> (this compound may be converted into the corresponding tropic acid ester), 2-acetyl -3- hydroxymethyl-pyridine, 2-aldehydro- 3-hydroxymethyl-pyridine, dihydrocodeinol ketone of the formula <FORM:0978680/C1/5> keto-reserpine of the formula <FORM:0978680/C1/6> b -(N-ethyl, N-acetyl) amino -a - phenylethyl alcohol, 1-(p-chloro -a - phenylbenzyl)-4-[a (2-acetoxyethyl)] piperazine and propionyl-(b -hydroxy -g - chloro-propyl) sulphide. 4-Amino-undecylenic alcohol is prepared by reducing the corresponding 4-oximino compound with lithium aluminium hydride. By a similar method the following are prepared: 4-amino- -9- octadecen -1- ol (may be converted into the corresponding trimethyl ammonium quaternary salt by reaction with methyl iodide), dihydrocodeinol amine of the formula <FORM:0978680/C1/7> and an amino-reserpine of the formula <FORM:0978680/C1/8> 1, 2-Hemiacetal of 2-hydroxymethylbenzaldehyde of the formula <FORM:0978680/C1/9> is prepared by treating 2-(oximinomethyl)-benzyl alcohol with nitrous acid. (The product may be converted to a mixed acetal of the formula <FORM:0978680/C1/100> By a similar method hemiacetals of the formulae <FORM:0978680/C1/111> and <FORM:0978680/C1/122> and the corresponding mixed acetal of the formulae <FORM:0978680/C1/133> and <FORM:0978680/C1/144> are prepared. An acetal of the formula <FORM:0978680/C1/155> is prepared by treating an oxime of the formula <FORM:0978680/C1/166> with acetic acid and sodium nitrite. The hydrazone of 3-hydroxymethyl-pyridine-2-aldehyde is prepared by treating 2-oximinomethyl-3-hydroxymethyl-pyridine with nitrous acid to form 3-hydroxymethyl-pyridine-2-aldehyde and then the hemiacetal thereof of the formula <FORM:0978680/C1/177> and treating the hemiacetal with hydrazine sulphate. The hydrozone of 2-acetyl -3- hydroxy-methyl-pyridine is prepared by a similar method. D 7,22-Ergostadiene-3b , 5a , 6b -triol 3-acetate is prepared by acetylating ergosterol to form the corresponding 3-acetate and treating the acetate with perphthalic acid. 6b -Hydroxystigmast -22- enyl acetate is prepared by acetylating stigmasterol to form the corresponding acetate, nitrating the acetate to form 6-nitro-stigmasterol acetate, reducing this compound with zinc dust and water to form 6-ketostigmast -22- enyl acetate and reducing this compound with sodium borohydride. Isorubijervine 3-acetate is prepared by treating isorubijervine with acetic anhydride. Estrone -3- acetate 11-18 hemiacetal of the formula <FORM:0978680/C1/188> is prepared by treating the corresponding 18-oxine of the formula <FORM:0978680/C1/199> with glacial acetic acid and sodium nitrite. By a similar method the following are prepared: aldosterone 21-acetatewhich may be converted to aldosterone, and the 11-18 hemiacetals of estradiol 3, 17-diacetate, D 4-androstene-3, 17-dione, androsterone, 17a -methyl-testosterone acetate, cortisol 21-acetate, 16a -acetoxycorticosterone 21-acetate, (16a - (and 16b )-methylcorticosterone 21-acetate, 16a -acetoxy -1- dehydrocorticosterone acetate, 16a (and 16b )-methyl -1- dehydrocorticosterone 21-acetate, pregnane -3a , 17a , 20b -triol-3, 30-diacetate, prednisolone acetate, 17a , acetoxyprogesterone, 16a - acetoxy - prednisolone 21-acetate, 16b -methyl-prednisolone acetate, 16a (and 16b )-methyl-D 1,4-pregnadiene-3, 20-dione-9a - fluoro-11b , 17a -dihydroxy -21- acetate, pregnane-3a , 11b , 20b -triol 3, 20-diacetate, and cholestanol -3- acetate. 18-Amino-testosterone acetate is prepared by reducing 11b -hydroxy -18- oximinotestosterone 17-acetate with lithium aluminium hydride and oxidising the reaction product with manganese dioxide and, if desired, reacting the 18-amino compound with methyl iodide to form a quaternary ammonium compound. 3b , 6b , 21-Trihydroxy -20- keto -5a - pregn-19-al-3, 21-diacetate 6, 19-hemi-acetal is prepared by treating the 19-oximino-3b , 21-diacetoxy -20-keto -5a - pregnane 6b -nitrite with glacial acetic acid and sodium nitrite, and the 6, 19-hemiacetals of the formulae <FORM:0978680/C1/200> <FORM:0978680/C1/211> are prepared by a similar method from the corresponding 19-oximino -6- hydroxy compound. The 6, 19-hemiacetal of the formula <FORM:0978680/C1/222> is prepared by reducing the corresponding 6-hydroxy -19- oximino compound with hydrazine and alkali. Steroid lactone of the formula <FORM:0978680/C1/233> is prepared by oxidising the corresponding 18-oxime of the formula <FORM:0978680/C1/244> with chromic acid in acetone. Similar lactones are prepared from 18-oximes of 11-hydroxy-progesterone. 11-Keto-strophanthridol 3-acetate is prepared by treating the corresponding 11-oxime with nitrous acid. Steroid aldehyde of the formula <FORM:0978680/C1/255> is prepared by treating the corresponding 19-oxime with chromous chloride and nitrous acid. By a similar method the following are prepared: 11b -hydroxy-4b , 5b -oxido-androstane-3, 17- dione 19-aldehyde (further treatment with chromous chloride forms an equilibrium mixture of D 4-androstene-3, 17-dione-11, 19-hemiacetal and 11b -hydroxy -D 4- androstene-3, 17-dione 19-aldehyde), and 4b , 5b -oxidohydrocorticosterone 21-acetate 19-aldehyde in equilibrium with the corresponding 11, 19-hemiacetal (further treatment with chromous chloride forms corticosterone 21-acetate 11, 19-hemiacetal). 2, 19-Hemiacetals of cholestanyl acetate is prepared by treating 2-hydroxy -19- oximinocholestanyl acetate with nitrous acid. The 4, 19-hemiacetal of cholesteryl acetate is prepared by a similar m
GB11823/60A 1960-04-04 1960-04-04 Organic nitrite esters and processes for the preparation of derivatives therefrom Expired GB978680A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB11823/60A GB978680A (en) 1960-04-04 1960-04-04 Organic nitrite esters and processes for the preparation of derivatives therefrom

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB11823/60A GB978680A (en) 1960-04-04 1960-04-04 Organic nitrite esters and processes for the preparation of derivatives therefrom

Publications (1)

Publication Number Publication Date
GB978680A true GB978680A (en) 1964-12-23

Family

ID=9993351

Family Applications (1)

Application Number Title Priority Date Filing Date
GB11823/60A Expired GB978680A (en) 1960-04-04 1960-04-04 Organic nitrite esters and processes for the preparation of derivatives therefrom

Country Status (1)

Country Link
GB (1) GB978680A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112154757A (en) * 2020-09-30 2021-01-01 福建泉智生物科技有限公司 Organic-inorganic matter balanced fertilization method for loquat

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112154757A (en) * 2020-09-30 2021-01-01 福建泉智生物科技有限公司 Organic-inorganic matter balanced fertilization method for loquat

Similar Documents

Publication Publication Date Title
GB996080A (en) 17-monoesters of 17ª‡,21-dihydroxy steroids and process for the preparation thereof
GB978680A (en) Organic nitrite esters and processes for the preparation of derivatives therefrom
US3215713A (en) Steroid nitrite esters
US2782193A (en) Process for the preparation of 16alpha, 17alpha-oxido-delta5-pregnene-3beta-ol-20-one
US2786855A (en) Oxidation of delta4-3, 6-dihydroxy steroids to delta4-3-keto-6-hydroxy steroids
GB1472922A (en) Pregnanoic acid derivatives
US3655649A (en) Process for the preparation of 19-norsteroids
GB931222A (en) Steroid compounds
DE1593052C3 (en) Process for the preparation of 16-methylene-19-norprogesterone derivatives
GB989881A (en) Improvements in or relating to 10 -methyl steroids and the production thereof
US2950291A (en) 17-oxygenated estra-1, 3, 5(10)-triene-1, 4-diols, their esters, and a corresponding quinone
US3065227A (en) 3alpha, 9alpha-epoxy steroids of the androstane and pregnane series
US2831872A (en) Synthesis of steroids
US3088952A (en) 1beta-cyano derivatives of delta4-3-keto pregnenes
US2791593A (en) Preparation of 21-acyloxy-20-ketopregnanes
US2773884A (en) Process for the manufacture of compounds of the steroid series
US2768186A (en) Process for preparing delta 8, 9-7-hydroxy steroids
GB892620A (en) Cyclopentanophenanthrene derivatives
US2885397A (en) 6beta-hydroxy-delta 4-3-keto steroids and process for the production thereof
GB857114A (en) Improvements in or relating to 16-substituted steroid compounds
US3247191A (en) 4beta, 19-oxido-steroids
US3113142A (en) Ring contraction process and products manufactured thereby
GB737773A (en) Improvements relating to 11-a-hydroxy-testosterone and esters thereof
Barnes et al. Methylsteroids. VII. Factors Affecting the Hydrolysis of 7α-and 11β-Acetoxylanostanes
US3060207A (en) Process for the manufacture of delta-16-alkyl-17alpha-hydroxy-pregnene-20-ones