USRE22944E - Nitro derivative of tertiary butyl - Google Patents
Nitro derivative of tertiary butyl Download PDFInfo
- Publication number
- USRE22944E USRE22944E US22944DE USRE22944E US RE22944 E USRE22944 E US RE22944E US 22944D E US22944D E US 22944DE US RE22944 E USRE22944 E US RE22944E
- Authority
- US
- United States
- Prior art keywords
- butyl
- tert
- hemimellitene
- tertiary butyl
- 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
- 150000002828 nitro derivatives Chemical class 0.000 title description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 title 1
- -1 butyl hemimellitene Chemical group 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-Trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 3
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 3
- SELSXVIZHNFFRV-UHFFFAOYSA-N 5-tert-butyl-2-(chloromethyl)-1,3-dimethylbenzene Chemical compound CC1=CC(C(C)(C)C)=CC(C)=C1CCl SELSXVIZHNFFRV-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000802 nitrating Effects 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N t-BuOH Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-Trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 1
- QZNVPEVKGGHBNS-UHFFFAOYSA-N 1,2-dimethyl-3-pentylbenzene Chemical group CCCCCC1=CC=CC(C)=C1C QZNVPEVKGGHBNS-UHFFFAOYSA-N 0.000 description 1
- FZSPYHREEHYLCB-UHFFFAOYSA-N 1-tert-butyl-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(C(C)(C)C)=C1 FZSPYHREEHYLCB-UHFFFAOYSA-N 0.000 description 1
- 240000007087 Apium graveolens Species 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-N Disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L Iron(II) chloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K Iron(III) chloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- XMWRWTSZNLOZFN-UHFFFAOYSA-N Musk xylene Chemical group CC1=C(N(=O)=O)C(C)=C(N(=O)=O)C(C(C)(C)C)=C1N(=O)=O XMWRWTSZNLOZFN-UHFFFAOYSA-N 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N Tert-Butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J Tin(IV) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J Titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
Definitions
- This invention relates to a nitro derivative of tertiary butyl hemimellitene and to a process for its manufacture.
- the tertiary butyl hemimellitene employed in the present process may be prepared according to any of the fololwing examples taken from my aforesaid application Serial No. 55,847:
- Example 1 65 g. tert-butyl chloride is added, with constant agitation, to a suspension of 5 g. anhydrous aluminum or ferric chloride in 300 g. pseudocumene at a temperature of about 510 C. When the reaction has subsided, the mixture is washed with water until free of acid and inorganic salts. The excess pseudocumene is distilled off and the remaining tert-butyl hemimellitene distilled in vacuo, the fraction boiling at 92 C. under a vacuum of 3.5 mm. being collected. By working at a higher temperature the iron or aluminum chloride may be replaced by tin or titanium tetrachloride,
- Example 2 To 1380 g. sulfuric acid 93%, previously cooled to C., there is added with eflicient agitation a solution of 120 g. tert-butyl alcohol in 410 g. pseudocumene, maintaining the temperature between 10 and 0 C. The reaction mixture is poured onto ice and the oil which separates 2 is washed free of acid and distilled as in Example 1.
- Example 3 1750 g. 1,3-dimethyl-5-tert-butyl benzene, hereafter referred to as butyl xylene, 108 g. Daraformaldehyde (or an equivalent quantity of commercial 37% formaldehyde solution) and 650 g. 31% hydrochloric acid are mixed and warmed to 50 C. Then with constant agitation there are added 1200 g. 82% sulfuric acid. After 5-6 hours agitation at 50-70 C. the formaldehyde is consumed and the reaction mixture is cooled.
- I may use the commercial grade of nitric acid analyzin 96-98% either with or without the addition of the commonly employed water removing agents such as sulfuric acid and acetic anhydride.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Reissued Dec. 2, 1947 p, Re. 22,944
F F l C E NITRO DERIVATIVE OF TERTIARY BUTYL HEMIMELLITENE AND PROCESS FOR PRE- PARING SAME Marion Scott Carpenter, Nutley, N. J assignor to Givaudan-Delawanna, Inc., New York, N. Y., a corporation of NewJersey No Drawing. Original No. 2,072,293, dated March 2, 1937, Serial No. 55,848, December 23, 1935. Application for reissue June 24, 1947, Serial No.
Claims.
This invention relates to a nitro derivative of tertiary butyl hemimellitene and to a process for its manufacture.
It is known that one of the nitro groups in musk xylene olHt CH3 can be replaced by COCH3, CN, CHO, N3 or halogen without destroying the characteristic musklike odor of the product. Prior to my discovery, however, it was not realized that one of the nitro groups in the above structural formula could be replaced by the methyl group to yield a product possessing a musk-like odor.
I have found that by nitrating tert-butyl hemimellitene, which was hitherto unknown, and the preparation of which is disclosed and claimed in my copending application, Serial No. 756,797, filed June 24, 1947, for the reissue of U. S. Patent No. 2,144,615, issued on application Serial No. 55,847, filed December 23, 1935, there is obtained a crystalline dinitro derivative having a musklike odor. Its structural formula is NO: OH:
The tertiary butyl hemimellitene employed in the present process may be prepared according to any of the fololwing examples taken from my aforesaid application Serial No. 55,847:
Example 1 65 g. tert-butyl chloride is added, with constant agitation, to a suspension of 5 g. anhydrous aluminum or ferric chloride in 300 g. pseudocumene at a temperature of about 510 C. When the reaction has subsided, the mixture is washed with water until free of acid and inorganic salts. The excess pseudocumene is distilled off and the remaining tert-butyl hemimellitene distilled in vacuo, the fraction boiling at 92 C. under a vacuum of 3.5 mm. being collected. By working at a higher temperature the iron or aluminum chloride may be replaced by tin or titanium tetrachloride,
Example 2 To 1380 g. sulfuric acid 93%, previously cooled to C., there is added with eflicient agitation a solution of 120 g. tert-butyl alcohol in 410 g. pseudocumene, maintaining the temperature between 10 and 0 C. The reaction mixture is poured onto ice and the oil which separates 2 is washed free of acid and distilled as in Example 1.
Example 3 1750 g. 1,3-dimethyl-5-tert-butyl benzene, hereafter referred to as butyl xylene, 108 g. Daraformaldehyde (or an equivalent quantity of commercial 37% formaldehyde solution) and 650 g. 31% hydrochloric acid are mixed and warmed to 50 C. Then with constant agitation there are added 1200 g. 82% sulfuric acid. After 5-6 hours agitation at 50-70 C. the formaldehyde is consumed and the reaction mixture is cooled. The acid layer is discarded, the oily layer is washed with water until free of acid and distilled, preferably in vacuo, The excess butyl Xylene distills over first then, under a vacuum of 4 mm. of mercury, there is collected the desired 2,6-dimethyl- 4-tert-butyl benzyl chloride boiling at 1l7-120 C. It, soon congeals to colorless, massive rhombs melting at about 26-27 C. The specific gravity at 25 C. of the super-cooled liquid is about 10030-10040. For the dechlorination of the 2,6- dimethyl-4-tert-butyl benzyl chloride it is not necessary that it be distilled from the excess butyl xylene; the crude product obtained from the above reaction may be submitted directly to the dechlorination process, although I prefer to remove the butyl xylene first. 355 g. zinc dust are covered with 500 a. water and the suspension heated to G. Then, with vigorous agitation there are introduced simultaneously the 2,6-dimethyl-4-tert-butyl benzyl chloride produced in the first step (either distilled or in the crude form containing butyl xylene) and 855 g. 18% sodium hydroxide solution. Stirring and refluxing are continued until the oily layer is free of chlorine. The oil is driven over with steam (or separated by decantation from the zinc slime) and redistilled as in Example 1.
For the nitration of the tert-butyl hemimellitene produced, for example, as described above I may use the commercial grade of nitric acid analyzin 96-98% either with or without the addition of the commonly employed water removing agents such as sulfuric acid and acetic anhydride.
The following example indicates in a general way the manner in which my invention may be put into practice, with the understanding that I do not limit myself to the specific quantities and conditions herein described:
To a mixture of 88 kgs, nitric acid 97% and 264 kgs. sulfuric acid 93% there is added with efiicient agitation 41 kgs. tort-butyl hemimellitene at a temperature of 20-35 C. The reaction mixture is poured onto crushed ice, the resulting crystals are filtered, taken up in benzene and the solution washed free of acid with an alkaline solution. The benzene is distilled OE and the remaining 3 crystals {are eewstaufiea from alcohol. suiting dinitro tert-butyl hemimellitene appears in the form of pale ellow glistening rods melting at 136-136.5 C. and having a musk-like odor.
The invention claimed is;
1. 2,6-dinitro-3,4,5-trimethi l I tr't butyi "Henzene, comprising yellow crystals of M. P. 136- 136.5 C. and having a musk' likeodor. 2. Process of preparing adinitroderivatit'epf uiiyl hemimellitene which comprises nitrat ing tert-butyl hemime11itene,
3. Process of preparing ammfirt tentative 6f tert-butyl hemimellitene which comprises "rem: ing nitric acid with tert-butyl hemimellitene and crystallizing the reaction mixture.
4. Process of preparing a dinitro derivative of tert-"butyl hemimellitene which comprises-reacting nitric acid with tert-butyl hemimellitene, crystallizing the reaction mixture, dissolving th resulting crystals in benzene and washing the 5. Process of preparing a dinitro derivative of hernim ellitene which comprises reacticl tert-butyl hemimellitene at El 20-35 C., crystallizing the reby'pouring on ice, dissolving the "fistals in benzene and washing the litioii free j of acid, distilling off the benzene and "'icrilstalliz'irig the product.
=MARI6N sco'r'r CARPENTER.
it' ii ifru-zl-zons CITED .Tlie following references are of record in the file of this patent:
Fusonetal fal; Am. Chem. Soc, VOL-63,4941, ee -2 B= a Darzens' et al., Comptes Rendus Acad. Sci-., vol. 99 (1934) ',.-pages '959 to 962.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE22944E true USRE22944E (en) | 1947-12-02 |
Family
ID=2089887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US22944D Expired USRE22944E (en) | Nitro derivative of tertiary butyl |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE22944E (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2955929A (en) * | 1958-03-18 | 1960-10-11 | Shell Oil Co | Weed killers |
-
0
- US US22944D patent/USRE22944E/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2955929A (en) * | 1958-03-18 | 1960-10-11 | Shell Oil Co | Weed killers |
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